Polyoxyalkylene polymer, method for producing polyoxyalkylene polymer, and curable composition

Abstract

The present invention provides a polyoxyalkylene polymer that has a hydrolyzable silyl group and that yields a curable composition having good curability, a method for producing said polyoxyalkylene polymer, a curable composition including said polyoxyalkylene polymer, and a cured product of said curable composition.　Provided is a polyoxyalkylene polymer having a hydrolyzable silyl group and a number average molecular weight of greater than 3000, wherein: (Na1+Na2) / Nt, which is the ratio of the sum of the number Na1 of hydrolyzable silyl groups (a1) having a specific structure and the number Na2 of hydrolyzable silyl groups (a2) having a specific structure to the sum Nt of the number of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups, is 0.60-1.00; and Na2 / Nt, which is the ratio of Na2 to Nt, is 0.03-1.00.

Description

Polyoxyalkylene polymer, method for producing polyoxyalkylene polymer, and curable composition

[0001] The present invention relates to a polyoxyalkylene polymer, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.

[0002] Organic polymers having at least one hydrolyzable silyl group in the molecule can be crosslinked by forming siloxane bonds accompanied by hydrolysis of the silyl group due to moisture or the like, even at room temperature. Polyoxyalkylene polymers having hydrolyzable silyl groups are widely used as such organic polymers. Organic polymers having hydrolyzable silyl groups are known to have the property of giving rubber-like cured products through such crosslinking reactions.

[0003] An organic polymer having a hydrolyzable silyl group is produced, for example, by a hydrosilylation reaction between an organic polymer having an allyl group at its terminal and a hydrosilane compound that provides a hydrolyzable silyl group. In this method, a Karstedt catalyst (platinum divinyldisiloxane complex) is often used as a catalyst for the hydrosilylation reaction (see, for example, Synthesis Example 2-1 of Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2021-75722

[0005] However, when a Karstedt catalyst is used as a catalyst for a hydrosilylation reaction, side reactions such as internal isomerization and hydrogenation occur in some cases. Therefore, it has been difficult to efficiently introduce a hydrolyzable silyl group having a structure corresponding to that of a hydrosilane compound into an organic polymer. Furthermore, there is room for further improvement in the reactivity of the resulting hydrolyzable silyl group. Furthermore, there is also room for improvement in the curing speed when a curable composition containing an organic polymer having such a hydrolyzable silyl group is cured.

[0006] Therefore, an object of the present invention is to provide a polyoxyalkylene polymer having a hydrolyzable silyl group that gives a curable composition with good curability, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that in a polyoxyalkylene polymer having hydrolyzable silyl groups and a number average molecular weight of more than 3,000, the total number N of the hydrolyzable silyl groups (a1) having a specific structure, the number of hydrolyzable silyl groups (a2) having a specific structure, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2). ａ２ and the ratio of the sum of (N ａ１ +N ａ２ ) / N ｔ is set to 0.60 or more and 1.00 or less, and N ｔ For N ａ２ The ratio of N ａ２ / N ｔ The present inventors have found that the above problems can be solved by adjusting the value of the saturation coefficient to 0.03 or more and 1.00 or less, and have completed the present invention.

[0008] That is, the present invention provides a polyoxyalkylene polymer having a hydrolyzable silyl group, wherein the polyoxyalkylene polymer has a number average molecular weight of more than 3,000, and the polyoxyalkylene polymer is represented by the following formula (1): (1) (In formula (1), R １ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R ２ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a is 0, 1, or 2.) The polyoxyalkylene polymer has hydrolyzable silyl groups (a1) represented by the following formula (I) and hydrolyzable silyl groups (a2) having a Si—H group, and the total number N of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2), the 1-propenyl groups, the propyl groups, and the allyl groups is ｔThe number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2). ａ２ and the ratio of the sum of (N ａ１ +N ａ２ ) / N ｔ is 0.60 or more and 1.00 or less, and N ｔ For N ａ２ The ratio of N ａ２ / N ｔ The polyoxyalkylene polymer has a molecular weight of 0.03 or more and 1.00 or less.

[0009] According to the present invention, it is possible to provide a polyoxyalkylene polymer having a hydrolyzable silyl group that gives a curable composition with good curability, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.

[0010] The present invention will be described in detail below.

[0011] <Polyoxyalkylene Polymer> The polyoxyalkylene polymer has a hydrolyzable silyl group. The polyoxyalkylene polymer has a number average molecular weight of more than 3,000. The polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the following formula (1) and a hydrolyzable silyl group (a2) having a Si—H group: (1) In formula (1), R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ２ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. a is 0, 1, or 2. In the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2), the 1-propenyl groups, the propyl groups, and the allyl groups is ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2). ａ２ and the ratio of the sum of (N ａ１ +N ａ２ ) / N ｔis 0.60 or more and 1.00 or less, and N ｔ For N ａ２ The ratio of N ａ２ / N ｔ is 0.03 or more and 1.00 or less.

[0012] A polyoxyalkylene polymer that satisfies the above conditions provides a curable composition with good curability.

[0013] As described above, the number-average molecular weight of the polyoxyalkylene polymer is greater than 3,000. Here, the number-average molecular weight is the polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). A cured product of a polyoxyalkylene polymer having such a molecular weight exhibits high modulus and high tensile strength. Therefore, a curable composition containing the polyoxyalkylene polymer can be suitably used as an adhesive, a sealant, an elastic coating agent, a pressure-sensitive adhesive, etc.

[0014] The number average molecular weight of the polyoxyalkylene polymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. There is no particular upper limit to the number average molecular weight of the polyoxyalkylene polymer. The number average molecular weight of the polyoxyalkylene polymer may be, for example, 100,000 or less, and preferably 50,000 or less. The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 100,000 or less, even more preferably 10,000 or more and 50,000 or less, and particularly preferably 20,000 or more and 50,000 or less. In addition, from the viewpoint of ease of handling of the polyoxyalkylene polymer and the curable composition containing the polyoxyalkylene polymer, the number average molecular weight of the polyoxyalkylene polymer is preferably not more than 10,000, more preferably not more than 6,000, and even more preferably not more than 4,000. In other words, from the viewpoint of ease of handling of the curable composition, the number average molecular weight of the polyoxyalkylene polymer (A) is preferably more than 3,000 and not more than 10,000, more preferably more than 30,000 and not more than 6,000, and even more preferably more than 3,000 and not more than 4,000.

[0015] The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polyoxyalkylene polymer is not particularly limited. It is preferable that the molecular weight distribution is narrow. Specifically, the molecular weight distribution is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, still more preferably 1.4 or less, and most preferably 1.3 or less. The weight average molecular weight is also measured by GPC.

[0016] The polyoxyalkylene polymer has a polyoxyalkylene skeleton, which is preferably a skeleton composed only of a plurality of oxyalkylene repeating units, or a skeleton composed only of a plurality of oxyalkylene repeating units and units derived from an initiator used in polymerization.

[0017] The number of carbon atoms in the oxyalkylene repeating unit is preferably 2 or more and 6 or less, and more preferably 2 or more and 4 or less.

[0018] The molecular chain structure of the polyoxyalkylene polymer may be either linear or branched.

[0019] The polyoxyalkylene polymer may contain linear molecules and branched molecules.

[0020] A linear molecule is preferred in that the cured product of a curable composition containing the polyoxyalkylene polymer described below has good elongation, whereas a branched molecule is preferred in that the curable composition of the polyoxyalkylene polymer described below has good strength.

[0021] The linear molecular structure is formed by ring-opening polymerization of a cyclic ether compound using an initiator having one or two hydroxyl groups per molecule, while the branched molecular structure is formed by ring-opening polymerization of an alkylene oxide using an initiator having three or more hydroxyl groups per molecule.

[0022] The polyoxyalkylene polymer skeleton is not particularly limited. Specific examples of suitable polyoxyalkylene polymer skeletons include a polyoxyethylene skeleton, a polyoxypropylene skeleton, a polyoxybutylene skeleton, a polyoxytetramethylene skeleton, a polyoxyethylene-polyoxypropylene copolymer skeleton, and a polyoxypropylene-polyoxybutylene copolymer skeleton. Of these skeletons, a polyoxypropylene skeleton is preferred. The polyoxyalkylene polymer may contain only molecules having one type of polyoxyalkylene skeleton, or may contain multiple types of molecules having different types of polyoxyalkylene skeletons.

[0023] When the curable composition containing the polyoxyalkylene polymer obtained by the above method is used as a sealant, adhesive, etc., the ratio of the mass of oxypropylene repeating units to the mass of the polyoxyalkylene skeleton in the polyoxyalkylene polymer is preferably 50 mass% or more, more preferably 80 mass% or more. In this case, the polyoxyalkylene polymer is amorphous. In addition, the viscosity of the polyoxyalkylene polymer tends to be low.

[0024] The polyoxyalkylene skeleton of the polyoxyalkylene polymer can be formed by ring-opening polymerization of a cyclic ether compound using a polymerization catalyst in the presence of an initiator according to a conventionally known method. Such ring-opening polymerization produces a polyoxyalkylene polymer having a hydroxyl group. Using the polyoxyalkylene polymer having a hydroxyl group as a raw material, the polyoxyalkylene polymer having a hydrolyzable silyl group can be obtained by the method described below.

[0025] Examples of methods for producing polyoxyalkylene polymers include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin disclosed in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, and 3,427,335, a polymerization method using a catalyst made of a polyphosphazene salt exemplified in JP-A-10-273512, and a polymerization method using a catalyst made of a phosphazene compound exemplified in JP-A-11-060722. A method of ring-opening polymerization of a cyclic ether compound using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it is easy to obtain a polyoxyalkylene polymer having a narrow molecular weight distribution (Mw / Mn).

[0026] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. As the cyclic ether compound, only one type may be used, or two or more types may be used in combination. Among the cyclic ether compounds, propylene oxide is particularly preferred because it is easy to obtain an amorphous, low-viscosity polyoxyalkylene polymer.

[0027] The initiator is not particularly limited. Specific preferred examples of the initiator include monools such as butanol and propylene glycol monoalkyl ether, glycols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and triethylene glycol, and polyols having three or more hydroxyl groups such as glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol.

[0028] Alternatively, a hydroxyl-terminated polyoxyalkylene polymer having a number average molecular weight of 300 to 4000 can be used as the initiator. Specific examples of the hydroxyl-terminated polyoxyalkylene polymer include polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

[0029] The polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the following formula (1) and a hydrolyzable silyl group (a2) having a Si—H group. (1) In formula (1), R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ２ is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms; a is 0, 1, or 2.

[0030] The polyoxyalkylene polymer usually has a plurality of hydrolyzable silyl groups (a1). The plurality of hydrolyzable silyl groups (a1) in the polyoxyalkylene polymer may be the same group or two or more different groups. １ If there are multiple R １ may be the same group or two or more different groups. ２ If there are multiple R ２ may be the same group or two or more different groups.

[0031] The hydrolyzable silyl group (a1) and the hydrolyzable silyl group (a2) are introduced into the polyoxyalkylene polymer by a hydrosilylation reaction between the polyoxyalkylene polymer having an allyl group and a hydrosilane compound. As the hydrosilane compound, a compound represented by the following formula (1-1) is used. In formula (1-1), R １ , R ２ , and a is R in formula (1). １ , R ２ , and a. HSiR １ ａ (OR ２ ) ３－ａ (1-1) The hydrosilane compound represented by formula (1-1) undergoes a hydrosilylation reaction with an allyl group in a polyoxyalkylene polymer to give a hydrolyzable silyl group (a1) represented by formula (1).

[0032] Furthermore, in the hydrosilylation reaction between the hydrosilane compound represented by formula (1-1) and the allyl group of the polyoxyalkylene polymer, a hydrolyzable silyl group (a2) having a Si—H group is generated. The structure of the hydrolyzable silyl group (a2) is not particularly limited. An example of the structure of the hydrolyzable silyl group (a2) is a structure represented by the following formula (2): (2) In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２The same applies to a and a. n is an integer of 0 or more. In formula (2), the upper limit of n is not particularly limited, and n is usually 10 or less.

[0033] The group represented by formula (2) is derived from a hydrosilane compound having a structure represented by formula (3) below, which is produced by condensation of two or more molecules of a hydrosilane compound represented by formula (1-1). The group represented by formula (2) is produced by a hydrosilylation reaction between the hydrosilane compound represented by formula (3) and an allyl group in a polyoxyalkylene polymer. In formula (3), there is no particular upper limit for n, and n is usually 10 or less. (3) In formula (3), R １ , R ２ , and a is R in formula (1). １ , R ２ , and a are the same as above. n is an integer of 0 or more.

[0034] A preferred example of the hydrolyzable silyl group (a2) having a Si—H group is a group represented by the following formula (4): When the hydrosilane compound (B) is modified by a disproportionation reaction into a hydrosilane compound having multiple Si—H groups in one molecule, the modified hydrosilane compound undergoes a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer (A) to produce a group represented by the following formula (4): (4) In formula (4), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as above. b is 1 or 2. a+b is 1 or more and 3 or less. The polyoxyalkylene polymer having a hydrolyzable silyl group (a2) having a Si—H group has good curability due to the high reactivity of the Si—H group.

[0035] Furthermore, the polyoxyalkylene polymer having the hydrolyzable silyl group (a1) and the hydrolyzable silyl group (a2) may have one or more of an allyl group, a 1-propenyl group, and a propyl group. The allyl group is an unreacted allyl group. The 1-propenyl group can be produced by an internal isomerization reaction of the allyl group as a side reaction. The propyl group can be produced by a hydrogenation reaction of the allyl group as a side reaction.

[0036] In the above formula (1) and formula (4), the oxygen atom bonded to the trimethylene group is bonded to any position in the polyoxyalkylene skeleton of the polyoxyalkylene polymer. The bonding position of the oxygen atom is not particularly limited. The oxygen atom may be bonded not only to the terminal of the polyoxyalkylene skeleton, but also to a position other than the terminal of the polyoxyalkylene skeleton. The bonding position of the oxygen atom is preferably only to the terminal of the polyoxyalkylene skeleton.

[0037] In formula (1) and formula (4), R １ , and R ２ R are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. １ , and R ２ The hydrocarbon group as R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ , and R ２ The hydrocarbon group as R may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. １ , and R ２ The structure of the aliphatic hydrocarbon group constituting the hydrocarbon group as R may be linear, branched, cyclic, or a combination of these structures. １ , and R ２ The number of carbon atoms in the hydrocarbon group as is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, even more preferably 1 or more and 6 or less, even more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

[0038] R １ , and R ２When the hydrocarbon group has a substituent, the type of the substituent is not particularly limited as long as the desired effect is not impaired. Specific examples of the substituent include halogen atoms such as chlorine and bromine, alkoxy groups such as methoxy and ethoxy, and substituted or unsubstituted amino groups such as amino, N-methylamino, N-ethylamino, N,N-dimethylamino, and N,N-diethylamino.

[0039] R １ , and R ２ Specific examples of the substituted or unsubstituted hydrocarbon group as the substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a 2-ethylhexyl group, and an n-dodecyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; substituted alkyl groups such as a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group; alkenyl groups such as a vinyl group, an isopropenyl group, and an allyl group; aryl groups such as a phenyl group, a toluyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group; and aralkyl groups such as a benzyl group and a phenethyl group.

[0040] Of the above-mentioned substituted or unsubstituted hydrocarbon groups, alkyl groups and substituted alkyl groups are preferred, with methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups being more preferred, and methyl groups being particularly preferred.

[0041] In formula (1) and formula (4), a is 0, 1, or 2. In terms of curability, a is preferably 0 or 1. Furthermore, in formula (4), b is 1 or 2. a+b is 1 or more and 3 or less. Therefore, 3-a-b is 0 or more and 2 or less.

[0042] In the group represented by formula (1), —SiR １ ａ (OR ２ ) ３－ａPreferred specific examples of the group represented by the formula (I) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, an (N,N-diethylaminomethyl)dimethoxysilyl group, and an (N,N-diethylaminomethyl)diethoxysilyl group.

[0043] Of these groups, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and (methoxymethyl)dimethoxysilyl are preferred, as they are more likely to give a cured product with good mechanical properties. １ ａ (OR ２ ) ３－ａ As the group represented by the formula (I), a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are preferred, and a trimethoxysilyl group and a (methoxymethyl)dimethoxysilyl group are more preferred. １ ａ (OR ２ ) ３－ａ As the group represented by the formula (I), a dimethoxymethylsilyl group and a triethoxysilyl group are more preferred, and a dimethoxymethylsilyl group is particularly preferred.

[0044] In addition, in the group represented by formula (4), —SiR １ ａ H ｂ (OR ２ ) ３－ａ－ｂ is a group represented by -SiR in the group represented by formula (1). １ ａ (OR ２ ) ３－ａ Among the groups represented by the formula: ２ It is preferable that the group represented by formula (4) is a group substituted with a hydrogen atom. １ ａ Hｂ (OR ２ ) ３－ａ－ｂ Specific examples of the group represented by the formula (I) include a dimethoxyhydrosilyl group, a methoxydihydrosilyl group, a diethoxyhydrosilyl group, a diethoxyhydrosilyl group, a di(2-propenyloxy)hydrosilyl group, a 2-propenyloxydihydrosilyl group, and a methoxy(methyl)hydrosilyl group (—SiCH ３ H (OCH ３ )), methyldihydrosilyl group, ethoxy(methyl)hydrosilyl group (—SiCH ３ H (OCH ２ CH ３ )), methoxy(ethyl)hydrosilyl group (—Si(CH ２ CH ３ ) H(OCH ３ )), ethyldihydrosilyl group, methoxy(chloromethyl)hydrosilyl group, chloromethyldihydrosilyl group, ethoxy(chloromethyl)hydrosilyl group, methoxy(methoxymethyl)hydrosilyl group, methoxymethyldihydrosilyl group, ethoxy(methoxymethyl)hydrosilyl group, methoxy(N,N-diethylaminomethyl)hydrosilyl group, N,N-diethylaminomethyldihydrosilyl group, and ethoxy(N,N-diethylamino)hydrosilyl group.

[0045] In the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2), the 1-propenyl groups, the propyl groups, and the allyl groups ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2). ａ２ and the ratio of the sum of (N ａ１ +N ａ２ ) / N ｔ is 0.60 or more and 1.00 or less. ｔ For N ａ２ The ratio of N ａ２ / N ｔ is 0.03 or more and 1.00 or less. (N ａ１ +N ａ２ ) / N ｔ And, N ａ２ / N ｔWhen the above and the above are within the above ranges, the curable composition containing the polyoxyalkylene polymer is cured quickly.

[0046] (N ａ１ +N ａ２ ) / N ｔ is preferably 0.70 or more and 1.00 or less, more preferably 0.80 or more and 1.00 or less, even more preferably 0.85 or more and 1.00 or less, even more preferably 0.90 or more and 1.00 or less, and most preferably 0.95 or more and 1.00 or less. ａ２ / N ｔ is preferably 0.10 or more and 1.00 or less, more preferably 0.20 or more and 1.00 or less, and even more preferably 0.25 or more and 1.00 or less. ａ２ / N ｔ may be 0.70 or less, may be 0.50 or less, may be 0.40 or less, or may be 0.30 or less.

[0047] N ａ１ / N ｔ , and N ａ２ / N ｔ teeth, １ The H NMR can be used to determine the ratio of the hydrolyzable silyl group (a1), the hydrolyzable silyl group (a2), the 1-propenyl group, the propyl group, and the allyl group based on the integral values ​​of the signals corresponding to the groups. For example, using a sample prepared by dissolving a polyoxyalkylene polymer having a hydrolyzable silyl group in deuterated chloroform, １ When H NMR measurement is performed, the peaks of the hydrolyzable silyl group (a1), the hydrolyzable silyl group (a2), the 1-propenyl group, the propyl group, and the allyl group are clearly distinguishable.

[0048] For example, for a 3-(dimethoxymethylsilyl)propyloxy group, which is an example of the hydrolyzable silyl group (a1), peaks derived from two protons are observed near 0.6 ppm. For an Si—H group, a peak derived from one proton is observed near 4.5 ppm. For an Si—H group derived from the starting hydrosilane compound, a peak derived from one proton is observed near 4.5 ppm. These peaks can be distinguished because the former does not decrease upon removal under reduced pressure, while the latter easily decreases or disappears upon removal under reduced pressure. Furthermore, for a peak derived from a 1-propenyl group, multiple peaks derived from one proton are observed near 5.9 to 6.3 ppm. Furthermore, a peak derived from a propyl group is observed as a peak derived from three protons near 0.9 ppm. Furthermore, a peak derived from an allyl group is observed as two peaks derived from two protons near 5.1 to 5.3 ppm. The above ratio can be determined based on the integrals of these peaks.

[0049] The method for producing a polyoxyalkylene polymer will be described in detail below. The polyoxyalkylene polymer is produced by a hydrosilylation reaction using a hydrosilylation catalyst. The hydrosilylation catalyst is not particularly limited, and examples include metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, as well as complexes of the aforementioned metals. However, by carrying out the hydrosilylation reaction in the presence of a ruthenium complex, in particular, a polyoxyalkylene polymer having a high content of hydrolyzable silyl groups is easily obtained. For this reason, the polyoxyalkylene polymer may contain a hydrosilylation catalyst such as a ruthenium complex used as a catalyst.

[0050] <<Method for Producing Polyoxyalkylene Polymer>> The polyoxyalkylene polymer described above can be produced by a method comprising hydrosilylation of an allyl group-containing polyoxyalkylene polymer (A) with a hydrosilane compound (B) in the presence of a hydrosilylation catalyst (C).

[0051] The allyl group-containing polyoxyalkylene polymer (A) is prepared using a hydroxyl group-containing polyoxyalkylene polymer obtained by ring-opening polymerization of a cyclic ether compound by the method described above.

[0052] In order to introduce allyl groups into the hydroxyl groups of the polyoxyalkylene polymer, the hydroxyl groups are reacted with an alkali metal compound to convert the hydroxyl groups into alkali metal alcoholates. A composite metal cyanide complex catalyst can also be used instead of the alkali metal compound.

[0053] Specific examples of alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide. Among these, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. In terms of availability, sodium methoxide is particularly preferred. In terms of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal compound may be subjected to the reaction in the form of a solution.

[0054] The amount of the alkali metal compound used is not particularly limited as long as it can introduce a desired number of allyl groups into the hydroxyl groups of the polyoxyalkylene polymer. The amount of the alkali metal compound used is preferably 0.5 mol or more, more preferably 0.6 mol or more, even more preferably 0.7 mol or more, and even more preferably 0.8 mol or more, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer. The amount of the alkali metal compound used is preferably 1.2 mol or less, more preferably 1.1 mol or less, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer. Therefore, the amount of the alkali metal compound used is preferably 0.5 mol or more to 1.2 mol or less, more preferably 0.6 mol or more to 1.2 mol or less, more preferably 0.7 mol or more to 1.1 mol or less, and particularly preferably 0.8 mol or more to 1.1 mol or less, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer.

[0055] In order to ensure that the reaction between the hydroxyl groups of the polyoxyalkylene polymer and the alkali metal compound proceeds smoothly, it is preferable to remove water and alcohol other than the polyoxyalkylene polymer having hydroxyl groups from the reaction solution containing the polyoxyalkylene polymer and the alkali metal compound in advance. Various known methods can be used to remove water and alcohol. Specifically, a method selected from the group consisting of thermal evaporation, reduced pressure devolatilization, spray evaporation, thin film evaporation, and azeotropic devolatilization can be used.

[0056] The temperature at which the hydroxyl groups of the polyoxyalkylene polymer are reacted with the alkali metal compound is not particularly limited as long as the reaction proceeds smoothly. The reaction temperature is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 145° C. or lower. The reaction time between the hydroxyl groups of the polyoxyalkylene polymer and the alkali metal compound is preferably 10 minutes or higher and 5 hours or lower, more preferably 30 minutes or higher and 3 hours or lower.

[0057] The polyoxyalkylene polymer (A) having allyl groups can be obtained by reacting the polyoxyalkylene polymer, whose hydroxyl groups have been converted to alkali metal alcoholates as described above, with an allyl halide.

[0058] Specific examples of allyl halides include allyl chloride, allyl bromide, allyl iodide, etc. Among these, allyl chloride is preferred from the viewpoint of ease of handling.

[0059] The amount of allyl halide used is not particularly limited as long as a desired amount of allyl groups is introduced into the polyoxyalkylene polymer. The amount of allyl halide used is preferably 0.7 mol or more, more preferably 1.0 mol or more, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer used to prepare the alkali metal alcoholated polyoxyalkylene polymer. The amount of allyl halide used is preferably 5.0 mol or less, more preferably 2.0 mol or less, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer used to prepare the alkali metal alcoholated polyoxyalkylene polymer. Therefore, the amount of allyl halide used is preferably 0.7 mol or more and 5.0 mol or less, more preferably 1.0 mol or more and 2.0 mol or less, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer used to prepare the alkali metal alcoholated polyoxyalkylene polymer.

[0060] The reaction temperature of the alkali metal alcoholated polyoxyalkylene polymer with the allyl halide 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 of the alkali metal alcoholated polyoxyalkylene polymer with the allyl halide is preferably 10 minutes or higher and 5 hours or lower, more preferably 30 minutes or higher and 3 hours or lower.

[0061] The polyoxyalkylene polymer (A) having an allyl group obtained as described above is subjected to hydrosilylation with a hydrosilane compound (B) in the presence of a ruthenium complex (C1) to produce a polyoxyalkylene polymer having a hydrolyzable silyl group.

[0062] The polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the above formula (1) and a hydrolyzable silyl group (a2) having a Si—H group.

[0063] For this reason, a compound represented by the following formula (1-1) is used as the hydrosilane compound (B): HSiR １ ａ (OR ２ ) ３－ａ (1-1) The hydrosilane compound (B) represented by formula (1-1) undergoes a hydrosilylation reaction with an allyl group contained in the polyoxyalkylene polymer (A) to produce a hydrolyzable silyl group (a1) represented by formula (1). In the hydrosilylation reaction between the hydrosilane compound (B) represented by formula (1-1) and the allyl group contained in the polyoxyalkylene polymer (A), a disproportionation reaction of the hydrosilane compound (B) occurs. When the hydrosilane compound having multiple Si—H groups per molecule produced by the disproportionation reaction further undergoes a hydrosilylation reaction with the allyl group, a hydrolyzable silyl group (a2) represented by formula (4) is produced.

[0064] In the above method, hydrosilylation is carried out in the presence of a hydrosilylation catalyst (C) such as a ruthenium complex (C1), thereby producing a desired amount of hydrolyzable silyl groups (a2) together with the hydrolyzable silyl groups (a1).

[0065] Specific examples of the hydrosilane compound (B) represented by formula (1-1) include trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, and diphenoxymethylsilane.

[0066] In terms of the curability of the polyoxyalkylene polymer finally obtained and the strength of the cured product of the curable composition containing the polyoxyalkylene polymer, trimethoxysilane and dimethoxymethylsilane are particularly preferred as the hydrosilane compound (B).

[0067] The amount of the hydrosilane compound used is preferably 1.0 mol or more, more preferably 3.0 mol or more, and even more preferably 5.0 mol or more, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (A). The amount of the hydrosilane compound used is preferably 20.0 mol or less, and more preferably 10.0 mol or less, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (A). Therefore, the amount of the hydrosilane compound used is preferably 1.0 mol or more and 20.0 mol or less, more preferably 3.0 mol or more and 20.0 mol or less, and even more preferably 5.0 mol or more and 10.0 mol or less, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (B). Using the hydrosilane compound (B) in an amount within the above range facilitates the production of a polyoxyalkylene polymer that is low in viscosity and easy to handle. The hydrosilane compound (B) used in the hydrosilylation reaction may be one type or two or more types.

[0068] The hydrosilylation reaction described above is carried out in the presence of a hydrosilylation catalyst (C). The hydrosilylation catalyst is not particularly limited, and examples thereof include metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, as well as complexes thereof. However, by carrying out the hydrosilylation reaction in the presence of a ruthenium complex (C1), in particular, a polyoxyalkylene polymer having a high content of hydrolyzable silyl groups is easily obtained.

[0069] The ruthenium complex (C1) is not particularly limited as long as it is a complex containing a ruthenium atom and is a complex compound that effectively promotes the above-mentioned hydrosilylation reaction.

[0070] The ruthenium complex (C1) is preferably a complex compound having a ligand (C2) derived from compound (D). Compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group per molecule. Here, the carbon-carbon double bond in compound (D) may be an ethylenic carbon-carbon double bond or an aromatic carbon-carbon double bond. Furthermore, in compound (D), at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.

[0071] The ruthenium complex (C1) may have one or more types of ligand (C2).

[0072] Examples of the electron-withdrawing group contained in compound (D) include halogen atoms such as a fluoro group, a chloro group, a bromo group, and an iodo group, a cyano group, an aldehyde group, and a nitro group. When multiple electron-withdrawing groups are present in the same molecule, the multiple electron-withdrawing groups may be the same or different. Compound (D) has one or more, preferably two or more, more preferably two to four, and even more preferably two or three electron-withdrawing groups in one molecule.

[0073] The electron-withdrawing group is preferably a halogen atom, and more preferably one or more selected from the group consisting of a fluoro group, a bromo group, and an iodo group. The electron-withdrawing group is more preferably a bromo group or an iodo group, and even more preferably a bromo group. In particular, compound (D) preferably has one or more, more preferably two or more, electron-withdrawing groups selected from a fluoro group, a bromo group, and an iodo group per molecule. Compound (D) preferably has one or more electron-withdrawing groups selected from a bromo group and an iodo group per molecule. In this case, compound (D) may have a fluoro group in addition to a bromo group and / or an iodo group. These electron-withdrawing groups are directly bonded to the carbon atoms constituting the carbon-carbon double bond in compound (D).

[0074] Compound (D) typically includes compounds having a cyclic skeleton. The cyclic skeleton may be a monocyclic skeleton consisting of only one monocycle, such as a cyclooctadiene skeleton, a benzene ring skeleton, or a cyclooctadiene skeleton; a polycyclic skeleton in which two or more monocycles are fused or bonded via a single bond, such as a naphthalene ring skeleton or a biphenyl skeleton; or an aliphatic cyclic skeleton having a bridge, such as a norbornadiene ring. Substituents such as the electron-withdrawing groups described above may be bonded to these skeletons. For example, 1,4-dibromobenzene is a compound having a benzene ring skeleton bonded to a bromo group as a substituent. Compound (D) is preferably a compound having a norbornadiene skeleton, a cyclooctadiene skeleton, a benzene ring skeleton, or a benzoquinone skeleton. More specifically, compounds having a 2,5-norbornadiene skeleton, a 1,5-cyclooctadiene skeleton, a p-cymene skeleton, a mesitylene skeleton, a benzene ring skeleton, or a benzoquinone skeleton are preferred, and compounds having a benzene ring skeleton or a norbornadiene skeleton are more preferred. The benzene ring skeleton is a skeleton consisting of one benzene ring, and the norbornadiene skeleton is a skeleton consisting of one norbornadiene ring.

[0075] Specific preferred examples of compound (D) include 2-bromonorbornadiene, 2,3-dibromonorbornadiene, 1,4-dibromobenzene, structural isomers of 1,4-dibromobenzene, 1,3,5-tribromobenzene, structural isomers of 1,3,5-tribromobenzene, 1,2,4,5-tetrabromobenzene, structural isomers of 1,2,4,5-tetrabromobenzene, hexabromobenzene, 1-bromo-3,5- Difluorobenzene, structural isomers of 1-bromo-3,5-difluorobenzene, 1-bromo-3,5-dichlorobenzene, structural isomers of 1-bromo-3,5-dichlorobenzene, 1-bromo-3-chloro-5-fluorobenzene, structural isomers of 1-bromo-3-chloro-5-fluorobenzene, 1,4-diiodobenzene, structural isomers of 1,4-diiodobenzene, 1,3,5-triiodobenzene, 1,3, Structural isomers of 5-triiodobenzene, 1,2,4,5-tetraiodobenzene, structural isomers of 1,2,4,5-tetraiodobenzene, hexaiodobenzene, 1,3-difluoro-5-iodobenzene, structural isomers of 1,3-difluoro-5-iodobenzene, 1,3-dichloro-5-iodobenzene, structural isomers of 1,3-dichloro-5-iodobenzene, 1,3-dibromo-5-iodobenzene, structural isomers of 1,3-dibromo-5-iodobenzene, 1-chloro-3-fluoro-5-iodobenzene, structural isomers of 1-chloro-3-fluoro-5-iodobenzene, 1-bromo-3-chloro-5-iodobenzene, structural isomers of 1-bromo-3-chloro-5-iodobenzene, 1-bromo-3-fluoro-5-iodobenzene, and structural isomers of 1-bromo-3-fluoro-5-iodobenzene.

[0076] Among these compounds, one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene are preferred as compound (D) in terms of the efficiency of conversion of an allyl group to a hydrolyzable silyl group (a1) and a hydrolyzable silyl group (a2).

[0077] Ruthenium complex (C1) can be produced by a known production method. Examples of raw materials for ruthenium complex (C1) include anhydrides and hydrates of compounds selected from ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. For example, ruthenium complex (C1) can be specifically produced by the following production method. First, compound (D) is added to an ethanol solution of ruthenium(III) chloride hydrate, and the mixture is heated under reflux. The solid matter in the reaction solution is then recovered by filtration. The recovered solid matter is dried to obtain ruthenium complex (C1). When ruthenium(III) chloride hydrate is used as a raw material, a basic compound such as sodium carbonate or sodium bicarbonate may be added to the reaction solution and the mixture may be heated under reflux to neutralize hydrogen chloride generated during heating under reflux. When ruthenium (III) chloride hydrate is reacted with compound (D), it is preferable to use compound (D) in an amount of 1 molar equivalent or more relative to the starting ruthenium compound, from the viewpoint of the reaction rate.

[0078] The ruthenium complex (C1) may be a nanoparticle catalyst. The particle size (cumulative median diameter) of the nanoparticles of the ruthenium complex (C1) is not particularly limited as long as the hydrosilylation reaction proceeds to the desired extent. The particle size is preferably 0.3 nm or more and 200 nm or less. The lower limit of the particle size is preferably 0.5 nm or more, more preferably 1 nm or more. The upper limit of the particle size is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. Therefore, the particle size of the nanoparticles of the ruthenium complex (C1) is more preferably 0.5 nm or more and 100 nm or less, even more preferably 0.5 nm or more and 50 nm or less, and particularly preferably 1 nm or more and 10 nm or less. The cumulative median diameter can be measured using a transmission electron microscope (TEM).

[0079] The ruthenium complex (C1) may contain, in addition to the ligand (C2) derived from the compound (D), a ligand (C2) derived from a compound (D') that does not fall under the category of the compound (D). The compound (D') is a compound that can coordinate to a ruthenium atom and does not fall under the category of the compound (D). Specific examples of the ligand (C2) derived from the compound (D') include a coordinating organic solvent such as dimethylformamide, a 2,5-norbornadiene ligand, a 1,5-cyclooctadiene ligand, a p-cymene ligand, a mesitylene ligand, a benzene ligand, a carbonyl ligand, an isocyanide ligand, and an arene ligand.

[0080] When the ruthenium complex (C1) has both a ligand (C2) derived from the compound (D) and a ligand (C2) derived from the compound (D'), a higher proportion of the ligand (C2) derived from the compound (D) among all the ligands (C2) contained in the ruthenium complex (C1) is preferable because this allows allyl groups to be converted to hydrolyzable silyl groups (a1) and (a2) with higher selectivity in the hydrosilylation reaction. The ratio of the number of ligands (C2) derived from the compound (D) to the total number of ligands (C2) contained in the ruthenium complex (C1) is preferably 1 mol % or more and 100 mol % or less, more preferably 50 mol % or more and 100 mol % or less, even more preferably 70 mol % or more and 100 mol % or less, and particularly preferably 90 mol % or more and 100 mol % or less.

[0081] In addition, the aforementioned N ａ２ / N ｔ It is also preferred that the ruthenium complex (C1) contains a phosphorus-containing ligand, since this facilitates increasing the value of N. ａ２ / N ｔ A high value of means that the amount of hydrolyzable silyl groups (a2) in the polyoxyalkylene polymer is large. When the amount of hydrolyzable silyl groups (a2) in the polyoxyalkylene polymer is large, the curability of the curable composition containing the polyoxyalkylene polymer is particularly excellent.

[0082] The phosphorus-containing ligand is not particularly limited as long as the desired effect is not impaired. As the phosphorus-containing ligand, a phosphine ligand is preferred. The phosphine ligand is not particularly limited. The phosphine ligand may be a monodentate ligand, a bidentate ligand, or a tridentate ligand. Specific examples of phosphine ligands include tris-1,1,1-(diphenylphosphinomethyl)methane, tris-1,1,1-(diphenylphosphinomethyl)ethane, tris-1,1,1-(diphenylphosphinomethyl)propane, tris-1,1,1-(diphenylphosphinomethyl)butane, tris-1,1,1-(diphenylphosphinomethyl)2,2-dimethylpropane, tris-1,3,5-(diphenylphosphinomethyl)cyclohexane, tris-1,1,1-(dicyclohexylphosphinomethyl)ethane, tris-1,1,1-(dimethylphosphinomethyl)ethane, tris-1,1,1-(diethylphosphinomethyl)ethane, 1,5,9-triethyl-1,5-9-triphosphacyclododecane, 1,5,9-trimethylphosphinomethyl ... Examples of suitable phosphine ligands include tridentate phosphine ligands derived from phosphines such as phenyl-1,5-9-triphosphacyclododecane and bis(2-diphenylphosphinoethyl)phenylphosphine; bidentate phosphine ligands derived from phosphines such as bis-1,2-(diphenylphosphino)ethane, bis-1,3-(diphenylphosphino)propane, bis-1,4-(diphenylphosphino)butane, bis-1,2-(dimethylphosphino)ethane, bis-1,3-(diethylphosphino)propane, and bis-1,4-(dicyclohexylphosphino)butane; and monodentate phosphine ligands derived from phosphines such as tricyclohexylphosphine, trioctylphosphine, trimethylphosphine, tripyridylphosphine, and triphenylphosphine.

[0083] In view of the ease of preparation and availability of the ruthenium complex (C1), the phosphine ligand is preferably a trialkylphosphine ligand or a triarylphosphine ligand, more preferably a triarylphosphine ligand, and particularly preferably a triphenylphosphine ligand.

[0084] A preferred example of the ruthenium complex (C1) having a phosphine ligand is tris(triphenylphosphine)ruthenium(II) dichloride (RuCl ２ (PPh ３ ) ３ ) are listed.

[0085] When a ruthenium complex (C1) having a phosphine ligand is used, from the viewpoint of increasing the hydrosilylation reactivity, it is preferable to carry out the hydrosilylation in the presence of the ruthenium complex (C1) having a phosphine ligand and the above-mentioned compound (D). In this case, the amount of compound (D) used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per part by mass of the ruthenium complex (C1) having a phosphine ligand.

[0086] In the hydrosilylation reaction, a ruthenium compound (C'1) that does not have a ligand (C2) derived from compound (D) may be reacted with compound (D) in a reaction solution to produce a ruthenium complex (C1). Specific examples of the ruthenium compound (C'1) include ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. Furthermore, the ruthenium compound (C'1) may be a ruthenium complex that does not have a ligand (C2) derived from compound (D) and has a ligand (C2) derived from compound (D') that does not fall under compound (D).

[0087] The amount of the hydrosilylation catalyst (C) used in the hydrosilylation reaction is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, and even more preferably 1 ppm by mass or more, relative to the mass of the allyl group-containing polyoxyalkylene polymer (A). The amount of the hydrosilylation catalyst (C) used in the hydrosilylation reaction is preferably 10 ppm by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, relative to the mass of the allyl group-containing polyoxyalkylene polymer (A). The amount of the hydrosilylation catalyst (C) used in the hydrosilylation reaction may be from 0.01 to 10 ppm by mass, from 0.1 to 10 ppm by mass, from 1 to 10 ppm by mass, from 0.01 to 1 ppm by mass, from 0.1 to 1 ppm by mass, from 0.1 to 1 ppm by mass, or from 0.01 to 0.1 ppm by mass, relative to the mass of the allyl group-containing polyoxyalkylene polymer (A). When the amount of the hydrosilylation catalyst (C) used is within the above range, the allyl groups in the polyoxyalkylene polymer (A) can be converted with high efficiency into hydrolyzable silyl groups (a1) and (a2).

[0088] The hydrosilylation reaction may be carried out in the presence or absence of a solvent. When a solvent is used, the type of solvent is not particularly limited. A compound with which the raw materials and catalyst do not react is used as the solvent. Specific examples of suitable solvents include hydrocarbon solvents such as hexane, and halogenated hydrocarbon solvents such as dichloromethane. For the hydrosilylation reaction, it is preferable to use a solvent that is sufficiently dehydrated and deoxygenated.

[0089] The reaction temperature of the hydrosilylation reaction can be appropriately determined taking into consideration the reactivity (reaction rate), the heat resistance temperature of the reaction vessel, etc. The reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher. The reaction temperature is preferably 200°C or lower, and more preferably 150°C or lower. In other words, the reaction temperature is preferably 0°C or higher and 200°C or lower, more preferably 20°C or higher and 200°C or lower, and even more preferably 40°C or higher and 150°C or lower. The higher the reaction temperature, the more likely it is that the reaction will be completed in a shorter time and side reactions will be suppressed.

[0090] The reaction time for the hydrosilylation reaction is not particularly limited as long as the reaction proceeds to the desired extent. The reaction temperature is preferably from 5 minutes to 12 hours, more preferably from 10 minutes to 5 hours.

[0091] The hydrosilylation reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

[0092] It is also preferred that the hydrosilylation be carried out in the presence of the compound (D). That is, it is preferred that the hydrosilylation be carried out in the presence of the ruthenium catalyst (C) and the compound (D). In this case, allyl groups in the polyoxyalkylene polymer (B) are easily converted to the hydrolyzable silyl groups (a1) and (a2) with high efficiency.

[0093] After the polyoxyalkylene polymer is produced as described above, the polyoxyalkylene polymer is washed with water and, if necessary, volatile components are distilled off from the polyoxyalkylene polymer to obtain the polyoxyalkylene polymer.

[0094] <Curable Composition> The curable composition contains a polyoxyalkylene polymer having a hydrolyzable silyl group produced by the method described above. The curable composition also contains a curing catalyst as a component for curing the polyoxyalkylene polymer.

[0095] Components other than the polyoxyalkylene polymer that may be contained in the curable composition will be described below.

[0096] (Curing Catalyst) The curable composition contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl groups, that is, the curing reaction.

[0097] As the curing 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, a mixture thereof, or the like can be used as the curing catalyst.

[0098] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dibutyltin oxide with a phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and a reaction product of dioctyltin oxide with a silicate compound. Among these, dioctyltin compounds are preferred due to the growing concern about the environment in recent years.

[0099] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc. The metal carboxylate can be a combination of the following carboxylic acids and various metals.

[0100] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; and ketimine compounds.

[0101] 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.

[0102] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0103] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0104] Two or more different curing catalysts may be used in combination. For example, the reactivity of the curing reaction can be improved by using the above-mentioned amine compound in combination with a carboxylic acid or by using the above-mentioned amine compound in combination with an alkoxy metal.

[0105] The amount of the curing catalyst used is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and particularly preferably 0.01 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer. Depending on the type of curing catalyst, after the curable composition has cured, the curing catalyst may seep out onto the surface of the cured product, or the surface of the cured product may be contaminated with the curing catalyst. In such cases, the amount of the curing catalyst used is preferably 0.01 to 3.0 parts by mass per 100 parts by mass of the polyoxyalkylene polymer. In this case, the surface condition of the cured product can be maintained good while ensuring curability.

[0106] The curable composition may contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property adjusters, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, surface property improvers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, various additives may be added to the curable composition as needed for the purpose of adjusting the physical properties of the curable composition or the cured product. Examples of such additives include curability adjusters, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0107] (Filler) The curable composition can 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, silicic acid anhydride, hydrated silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.

[0108] The amount of the filler used is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 10 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0109] To reduce the weight (specific gravity) of the cured product, organic balloons and / or inorganic balloons may be added to the curable composition. Balloons are hollow spherical fillers. Examples of balloon materials include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0110] The amount of balloons used is preferably 0.1 parts by mass or more and 100 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0111] (Adhesion Imparting Agent) An adhesion imparting agent can be added to the curable composition. Examples of the adhesion imparting agent include silane coupling agents and reaction products of silane coupling agents.

[0112] 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, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyltriethoxysilane; Examples of suitable adhesion promoters include isocyanate group-containing silanes such as anthracene propylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes with other alkoxysilanes; and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes. The adhesion promoters may be used alone or in combination of two or more.

[0113] The amount of the silane coupling agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0114] (Plasticizer) A plasticizer can be added to the curable composition. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid 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 paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, and epoxy plasticizers such as epoxy benzyl stearate.

[0115] Furthermore, a polymer plasticizer can be used. Specific examples of the polymer plasticizer 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 hydroxy groups of these polyether polyols are converted into ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Only one type of plasticizer may be used, or two or more types may be mixed and used.

[0116] The polymeric plasticizer may or may not have a reactive silyl group. When the polymeric plasticizer has a reactive silyl group, the polymeric plasticizer acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product. When the polymeric plasticizer has a reactive silyl group, the average number of reactive silyl groups per molecule is preferably 1 or less, more preferably 0.8 or less. When a plasticizer having a reactive silyl group, particularly a polyoxyalkylene polymer having a reactive silyl group, is used as the plasticizer, the number-average molecular weight of the polyoxyalkylene polymer as the plasticizer is preferably lower than the number-average molecular weight of the polyoxyalkylene polymer contained therein.

[0117] The amount of the plasticizer used is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 120 parts by mass or less, and even more preferably 20 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0118] (Solvent, Diluent) A solvent or diluent may be added to the curable composition. The solvent or diluent is not particularly limited as long as the desired effect is not impaired. As the solvent or diluent, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used. When a solvent or diluent is used, in view of the problem of air pollution when the curable composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. Only one type of solvent or diluent may be used, or two or more types may be mixed and used.

[0119] (Anti-sagging agent) If necessary, an anti-sagging agent may be added to the curable composition to prevent sagging and improve workability. The anti-sagging agent is not particularly limited. Examples of the anti-sagging agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Only one type of anti-sagging agent may be used, or two or more types may be used in combination.

[0120] The amount of the anti-sagging agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the polyoxyalkylene polymer.

[0121] (Antioxidant) An antioxidant (antiaging agent) may be added to the curable composition. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds. For example, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), and BHT are examples of suitable antioxidants. Similarly, hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, and Adeka STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants that can be used include SONGNOX 4120, Nauguard 445, and OKABEST CLX050. Specific examples of antioxidants are also described in Japanese Patent Application Laid-Open Nos. 4-283259 and 9-194731.

[0122] The amount of the antioxidant used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0123] (Light stabilizer) A light stabilizer may be added to the curable composition. The use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of light stabilizers include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds. Hindered amine-based compounds are particularly preferred.

[0124] The amount of the light stabilizer used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the polyoxyalkylene polymer.

[0125] (Ultraviolet Absorber) An ultraviolet absorber may be added to the curable composition. Use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, substituted acrylonitrile-based compounds, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred. Suitable specific examples of 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).

[0126] The amount of the ultraviolet absorber used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0127] (Physical Property Modifier) ​​A physical property modifier may be added to the curable composition as needed for the purpose of adjusting the tensile properties of the resulting cured product. The physical property modifier is not particularly limited. Suitable specific examples of the physical property modifier 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 varnish; polysiloxane, and the like. The use of a physical property modifier can increase the hardness of the cured product, or conversely, decrease the hardness and improve the elongation at break of the cured product. The physical property adjusting agent may be used alone or in combination of two or more.

[0128] In particular, compounds that produce a compound having a monovalent silanol group 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 as such compounds. Examples of compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and that produce silane monool upon hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0129] The amount of the physical property adjuster used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0130] (Tackifying Resin) A tackifying resin may be added to the curable composition for the purpose of improving adhesion or adhesion to a substrate, or for other reasons. The tackifying resin is not particularly limited.

[0131] Specific examples of tackifying resins 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, hydrogenated styrene block copolymers, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins. Only one type of tackifying resin may be used, or two or more types may be mixed and used.

[0132] The amount of the tackifier resin used is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0133] (Epoxy Group-Containing Compound) An epoxy group-containing compound may be added to the curable composition. The use of an epoxy group-containing compound can improve the recovery of the cured product. Examples of epoxy group-containing compounds include epoxy compounds such as epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and epichlorohydrin derivatives, as well as mixtures thereof. Specific examples of epoxy group-containing compounds 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 group-containing compound is preferably used in an amount of 0.5 to 50 parts by mass per 100 parts by mass of the polyoxyalkylene polymer.

[0134] (Photocurable Substance) A photocurable substance may be added to the curable composition. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many photocurable substances are known, such as organic monomers, oligomers, resins, and compositions containing these. Representative photocurable substances include unsaturated acrylic compounds, such as monomers and oligomers having one or more acrylic unsaturated groups or one or more methacrylic unsaturated groups, and mixtures thereof; polyvinyl cinnamates; and azido resins.

[0135] The amount of the photocurable substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.

[0136] (Oxygen-Curable Substance) An oxygen-curable substance may be added to the curable composition. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. The oxygen-curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product, preventing surface stickiness 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; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, or silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5 to C8 dienes obtained by homopolymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. Only one type of oxygen-curable substance may be used, or two or more types may be mixed and used.

[0137] The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photo-curable substance.

[0138] (Epoxy Resin) The curable composition may contain an epoxy resin. The curable composition containing an epoxy resin is preferably used as an adhesive, and particularly preferably as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A epoxy resin and novolac epoxy resin.

[0139] The ratio of the epoxy resin to the polyoxyalkylene polymer used is preferably within the range of 100 / 1 to 1 / 100 in terms of the mass ratio of polyoxyalkylene polymer / epoxy resin.

[0140] When an epoxy resin is added to the curable composition, a curing agent for curing the epoxy resin may be added to the curable composition together with the epoxy resin. The epoxy resin curing agent is not particularly limited, and any commonly used epoxy resin curing agent can be used.

[0141] When a curing agent for epoxy resin is used, the amount of the curing agent used is preferably in the range of 0.1 parts by mass to 300 parts by mass per 100 parts by mass of the epoxy resin.

[0142] The curable composition described above is cured by a method appropriate for the intended use of the curable composition to form a cured product.

[0143] <Preparation of Curable Composition> The curable composition can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with a polymer composition containing a polyoxyalkylene polymer before use. From the viewpoint of workability, the one-component type is preferred.

[0144] When the curable composition is a one-component type, all of the components are blended in advance. For this reason, it is preferable that the components containing water are dehydrated and dried before use, or that they are dehydrated under reduced pressure or the like during blending and kneading. In addition to the dehydration and drying method, the storage stability of the curable composition can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane to the curable composition.

[0145] <<Uses of Curable Compositions>> The curable compositions can be used as architectural sealants, industrial adhesives, waterproof coating compositions, adhesive raw materials, and the like. They can also be used as sealants for buildings, ships, automobiles, roads, and the like. Furthermore, the curable compositions, alone or with the aid of a primer, can adhere to a wide range of substrates, including glass, porcelain, wood, metal, and resin moldings. Therefore, the curable compositions can also be used as various types of sealing and adhesive compositions. In addition to conventional adhesives, the curable compositions can also be used as contact adhesives. Furthermore, the curable compositions are useful as food packaging materials, cast rubber materials, molding materials, and paints. The cured products of the above curable compositions exhibit low water absorption. Therefore, the above curable compositions and their cured products are particularly suitable for waterproof materials, such as sealants, waterproof adhesives, and waterproof coatings.

[0146] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0147] That is, the present invention includes the following.

[0148] <1> A polyoxyalkylene polymer having a hydrolyzable silyl group, wherein the polyoxyalkylene polymer has a number average molecular weight of more than 3,000, and the polyoxyalkylene polymer is represented by the following formula (1): (1) (In formula (1), R １ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R ２ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a is 0, 1, or 2.) The polyoxyalkylene polymer has hydrolyzable silyl groups (a1) represented by the following formula (I) and hydrolyzable silyl groups (a2) having a Si—H group, and the total number N of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2), the 1-propenyl groups, the propyl groups, and the allyl groups is ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2). ａ２ and the ratio of the sum of (N ａ１ +N ａ２ ) / N ｔ is 0.60 or more and 1.00 or less, and N ｔ For N ａ２ The ratio of N ａ２ / N ｔ <2> A polyoxyalkylene polymer, wherein the hydrolyzable silyl group (a2) is a group represented by the following formula (4): (4) (In formula (4), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as those in the formula (1), b is 1 or 2, and a+b is 1 or more and 3 or less. ａ２ / N ｔ <4> The polyoxyalkylene polymer according to <1> or <2>, wherein N is 0.10 or more and 1.00 or less. ａ２ / N ｔ<5> The polyoxyalkylene polymer according to any one of <1> to <4>, which contains a ruthenium complex. <6> A method for producing the polyoxyalkylene polymer according to any one of <1> to <5>, which comprises hydrosilylation of an allyl-containing polyoxyalkylene polymer (A) with a hydrosilane compound (B) in the presence of a hydrosilylation catalyst (C). <7> A method for producing the polyoxyalkylene polymer according to <6>, in which the hydrosilylation catalyst (C) is a ruthenium complex (C1). <8> The method for producing a polyoxyalkylene polymer according to <7>, wherein the ruthenium complex (C1) has a ligand (C2) derived from a compound (D), the compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond. <9> The method for producing a polyoxyalkylene polymer according to <8>, wherein the compound (D) has a benzene ring skeleton or a norbornadiene skeleton. <10> The method for producing a polyoxyalkylene polymer according to <8> or <9>, wherein the compound (D) has, as the electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group. <11> The method for producing a polyoxyalkylene polymer according to any one of <8> to <10>, wherein the compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene. <12> The method for producing a polyoxyalkylene polymer according to any one of <7> to <11>, wherein the hydrosilylation is carried out in the presence of a compound (D), wherein the compound (D) has, in one molecule, at least one carbon-carbon double bond and at least one electron-withdrawing group, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.<13> The method for producing a polyoxyalkylene polymer according to <12>, wherein compound (D) has a benzene ring skeleton or a norbornadiene skeleton. <14> The method for producing a polyoxyalkylene polymer according to <12> or <13>, wherein compound (D) has at least one electron-withdrawing group selected from the group consisting of a fluoro group, a bromo group, and an iodo group. <15> The method for producing a polyoxyalkylene polymer according to any one of <12> to <14>, wherein compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene. <16> A method for producing a polyoxyalkylene polymer according to any one of <7> to <15>, wherein the ruthenium complex (C1) contains a phosphorus-containing ligand. <17> A method for producing a polyoxyalkylene polymer according to <16>, wherein the phosphorus-containing ligand is a triphenylphosphine ligand. <18> A method for producing a polyoxyalkylene polymer according to <16> or <17>, wherein the ruthenium catalyst (C1) is tris(triphenylphosphine)ruthenium(II) dichloride. <19> A curable composition comprising the polyoxyalkylene polymer according to any one of <1> to <5> and a curing catalyst. <20> A cured product of the curable composition according to <19>.

[0149] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF (tetrahydrofuran) Molecular weight: polystyrene equivalent Measurement temperature: 40°C

[0150] The proportions of silyl groups, 1-propenyl groups or propyl groups, and allyl groups were calculated using the following nuclear magnetic resonance (NMR) spectrometer: １ H NMR measurement was performed. Apparatus: AVANCE III HD500 digital instrument (manufactured by BRUKER)

[0151] (Skinning Time) In an atmosphere of 23°C and 50% relative humidity, 3 parts by mass of tin(II) bis(2-ethylhexanoate) (Nitto Kasei, Neostan U-28) as a curing catalyst and 0.5 parts by mass of laurylamine (Wako Pure Chemical Industries) were added to 100 parts by mass of each silyl group-containing organic polymer, and the mixture was stirred with a spatula for 1 minute. The time when mixing was completed was defined as the curing start time, and the time when the composition to be evaluated no longer adhered to the spatula when the surface was touched with the spatula was defined as the skinning time.

[0152] Synthesis Example 1 Using polyoxypropylene glycol having a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer (H-1) having a number-average molecular weight of 27,600 and hydroxyl groups at both ends. To the polymer (H-1), 1.1 mol equivalents of sodium methoxide relative to the hydroxyl groups of the polymer (H-1) was added as a 28% methanol solution. After removing the methanol from the resulting mixture by distillation under reduced pressure, 1.3 mol equivalents of allyl chloride relative to the hydroxyl groups of the polymer (H-1) was added and the reaction was carried out at 130°C for 1 hour. Thereafter, unreacted allyl chloride was removed by distillation under reduced pressure from the reaction solution. The resulting unpurified allyl group-containing polyoxyalkylene polymer was mixed and stirred with n-hexane and water, and the water was then removed by centrifugation. The hexane was removed from the resulting hexane solution by distillation under reduced pressure to remove metal salts from the polymer. In this way, an allyl group-containing polyoxyalkylene polymer (A-1) was obtained.

[0153] Example 1 100 ppm by mass of RuCl relative to the mass of the polymer (A-1) obtained in Synthesis Example 1 ２ (PPh ３ ) ３), and 260 ppm by mass of 2,3-dibromonorbornadiene relative to the mass of polymer (A-1) were added to polymer (A-1). 2,3-Dibromonorbornadiene is a compound having an electron-withdrawing group and capable of coordinating with ruthenium. The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in polymer (A-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in polymer (A-1) and dimethoxymethylsilane was carried out at 90°C. The reaction was continued for 1 hour from the start of the reaction. １ H NMR measurement was carried out to confirm that the allyl groups in the polymer (A-1) had completely disappeared. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-1). １ H NMR measurement was performed, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time of the obtained polymer (S-1) was measured by the method described above. The results are shown in Table 1.

[0154] Synthesis Example 2 To the polymer (A-1), 2400 ppm by mass of a commercially available Karstedt catalyst (platinum divinyldisiloxane complex (3 wt % isopropanol solution in terms of platinum)) and 5.0 mol equivalents of dimethoxymethylsilane hydrosilane relative to the allyl groups in the polymer (A-1) were added, and the hydrosilylation reaction of the polymer (A-1) with dimethoxymethylsilane was initiated at 90°C. Every hour from the start of the reaction, １ H NMR measurement was carried out to confirm that the allyl groups in the polymer (A-1) had completely disappeared. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-7). １H NMR measurement was carried out, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time of the obtained polymer (S-7) was measured by the above-mentioned method. The results are shown in Table 1.

[0155] (Examples 2 and 3) For the purpose of adjusting the ratio of the silyl group (a1) and the silyl group (a2), the polymer (S-1) obtained in Example 1 and the polymer (S-7) obtained in Synthesis Example 2 were mixed to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-2) of Example 2 and a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-3) of Example 3. For the obtained polymer (S-2) and polymer (S-3), １ H NMR measurement was carried out, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time was measured by the above-mentioned method using the obtained polymer (S-2) and polymer (S-3). The results are shown in Table 1.

[0156] Example 4 100 mass ppm of [RuCl] relative to the mass of polymer (A-1) ２ (nbd)] ｎ and 260 ppm by mass of 2,3-dibromonorbornadiene relative to the mass of polymer (A-1) were added to polymer (A-1). nbd is a 2,5-norbornadiene ligand. 2,5-norbornadiene ligands do not have an electron-withdrawing group. On the other hand, 2,3-dibromonorbornadiene is a compound that has an electron-withdrawing group and can coordinate to ruthenium. The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in polymer (A-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in polymer (A-1) and dimethoxymethylsilane was carried out at 90°C. The reaction was continued for 1 hour from the start of the reaction. １H NMR measurement was carried out to confirm that the allyl groups in the polymer (A-1) had completely disappeared. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-4). １ H NMR measurement was performed, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time of the obtained polymer (S-4) was measured by the method described above. The results are shown in Table 1.

[0157] Example 5: 240 ppm by mass of [RuCl] relative to the mass of polymer (A-1) ２ (p-cymene)] ｎ was added to the polymer (A-1). p-Cymene is a p-cymene ligand. The p-cymene ligand does not have an electron-withdrawing group. The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in the polymer (A-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in the polymer (A-1) and the dimethoxymethylsilane was carried out at 90°C. Every hour from the start of the reaction, １ H NMR measurement was carried out to confirm that the allyl groups in the polymer (A-1) had completely disappeared. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-5). １ H NMR measurement was performed, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time of the obtained polymer (S-5) was measured by the above-mentioned method. The results are shown in Table 1.

[0158] Synthesis Example 3 While stirring an ethanol solution containing 0.15 parts by mass of ruthenium(III) chloride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) under a nitrogen atmosphere, 0.064 parts by mass of sodium carbonate and 0.36 parts by mass of 2,3-dibromonorbornadiene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added under heating and reflux. The reaction solution was stirred under the above conditions for 1 hour, and then the solid content in the reaction solution was filtered off. The obtained solid content was dried under reduced pressure to obtain a ruthenium complex.

[0159] Example 6 The ruthenium complex obtained in Synthesis Example 3 was added to the polymer (A-1) in an amount of 240 ppm by mass relative to the mass of the polymer (A-1). The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in the polymer (A-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in the polymer (A-1) and the dimethoxymethylsilane was carried out at 90°C. Every hour from the start of the reaction, １ H NMR measurement was carried out, and it was confirmed that the allyl groups in the polymer (A-1) had completely disappeared. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-6). １ H NMR measurement was performed, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated. Furthermore, the skinning time of the obtained polymer (S-6) was measured by the above-mentioned method. The results are shown in Table 1.

[0160] (Comparative Example 1) To the polymer (S-1) obtained in Example 1, 3 parts by mass of methanol was added per 100 parts by mass of the polymer (S-1), and the mixture was reacted at 90°C for 1 hour. After that, the volatile components were distilled off under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-8). １ H NMR measurement was carried out, and it was confirmed that the silyl group (a2) represented by formula (4) in the polymer (S-1) was converted to the silyl group (a1) represented by formula (1) by this operation.１ H NMR measurement was carried out to calculate the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total number. Furthermore, the skinning time of the obtained polymer (S-8) was measured by the above-mentioned method.

[0161] The results are shown in Table 1.

[0162] Table 1 below shows the reaction conditions for the Examples and Comparative Examples. Table 1 also shows the ratios of functional groups in the polyoxyalkylene polymers obtained in the Examples and Comparative Examples. The compounds listed in Table 1 are compounds used together with the hydrosilylation catalyst. The hydrosilylation catalysts listed in Table 1 are as follows: Cat 1: RuCl ２ (PPh ３ ) ３ Cat2: [RuCl ２ (nbd)] ｎ Cat3: [RuCl ２ (p-cymene)] ｎ Cat 4: Ruthenium complex obtained in Synthesis Example 3 The compounds listed in Table 1 are as follows: Com 1: 2,3-dibromonorbornadiene The silyl group a1 listed in Table 1 is a hydrolyzable silyl group (a1) represented by formula (1). The silyl group a2 listed in Table 1 is a hydrolyzable silyl group (a2) represented by formula (4). *The functional group ratios in Table 1 are values ​​rounded to the first decimal place, so the total of the functional group ratios may not amount to 100%.

[0163] According to Table 1, the number N of hydrolyzable silyl groups (a1) ａ１ , the number N of hydrolyzable silyl groups (a2) ａ２ , the total number of 1-propenyl groups and the number of propyl groups, N ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ and the number N of hydrolyzable silyl groups (a2) ａ２ The ratio of the total (N ａ１ +N ａ２ ) / N ｔ And, N ｔ N forａ２ Ratio N ａ２ / N ｔ It can be seen that the polyoxyalkylene polymers of the Examples, in which the above-mentioned values ​​are within the above-mentioned ranges, give curable compositions that exhibit short skinning times and good curability.

[0164] On the other hand, according to Comparative Example 1, (N ａ１ +N ａ２ ) / N ｔ Even if N is within a predetermined range, ａ２ / N ｔ It is clear that the polyoxyalkylene polymer of Comparative Example 1, which is outside the specified range, only provides a curable composition that exhibits a long skinning time.

Claims

1. A polyoxyalkylene polymer having a hydrolyzable silyl group, the polyoxyalkylene polymer having a number average molecular weight of more than 3,000, the polyoxyalkylene polymer being represented by the following formula (1): (1) (In formula (1), R １ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R ２ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a is 0, 1, or 2. In the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ and the number N of the hydrolyzable silyl groups (a2). ａ２ The ratio of the sum of (N ａ１ +N ａ２ ) / N ｔ is 0.60 or more and 1.00 or less, ｔ For the N ａ２ The ratio of N ａ２ / N ｔ A polyoxyalkylene polymer having a molecular weight of 0.03 or more and 1.00 or less.

2. The hydrolyzable silyl group (a2) is represented by the following formula (4): (4) (In formula (4), R １ , R ２ , and a is R in formula (1). １ , R ２ 2. The polyoxyalkylene polymer according to claim 1 , wherein the alkyl group is a group represented by the following formula:

3. The above N ａ２ / N ｔ The polyoxyalkylene polymer according to claim 1 or 2, wherein the polyoxyalkylene polymer is 0.10 or more and 1.00 or less.

4. The above N ａ２ / N ｔ The polyoxyalkylene polymer according to claim 1 or 2, wherein the polyoxyalkylene polymer is 0.20 or more and 1.00 or less.

5. The polyoxyalkylene polymer according to claim 1 or 2, which contains a ruthenium complex.

6. A method for producing a polyoxyalkylene polymer according to claim 1 or 2, which comprises hydrosilylation of an allyl-containing polyoxyalkylene polymer (A) with a hydrosilane compound (B) in the presence of a hydrosilylation catalyst (C).

7. The method for producing a polyoxyalkylene polymer according to claim 6, wherein the hydrosilylation reaction catalyst (C) is a ruthenium complex (C1).

8. The method for producing a polyoxyalkylene polymer according to claim 7, wherein the ruthenium complex (C1) has a ligand (C2) derived from a compound (D), the compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.

9. The method for producing a polyoxyalkylene polymer according to claim 8, wherein the compound (D) has a benzene ring skeleton or a norbornadiene skeleton.

10. The method for producing a polyoxyalkylene polymer according to claim 8, wherein the compound (D) has, as the electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.

11. The method for producing a polyoxyalkylene polymer according to claim 8, wherein the compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene.

12. The method for producing a polyoxyalkylene polymer according to claim 7, wherein the hydrosilylation is carried out in the presence of a compound (D), the compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.

13. The method for producing a polyoxyalkylene polymer according to claim 12, wherein the compound (D) has a benzene ring skeleton or a norbornadiene skeleton.

14. The method for producing a polyoxyalkylene polymer according to claim 13, wherein the compound (D) has, as the electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.

15. The method for producing a polyoxyalkylene polymer according to claim 13, wherein the compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene.

16. The method for producing a polyoxyalkylene polymer according to claim 12, wherein the ruthenium complex (C1) contains a phosphorus-containing ligand.

17. The method for producing a polyoxyalkylene polymer according to claim 16, wherein the phosphorus-containing ligand is a triphenylphosphine ligand.

18. The method for producing a polyoxyalkylene polymer according to claim 16, wherein the ruthenium catalyst (C1) is tris(triphenylphosphine)ruthenium(II) dichloride.

19. A curable composition comprising the polyoxyalkylene polymer according to claim 1 or 2 and a curing catalyst.

20. A cured product of the curable composition according to claim 19.