Method for producing polyoxyalkylene-based polymer, polyoxyalkylene-based polymer, and curable composition

Abstract

Provided are: a method for producing a polyoxyalkylene-based polymer, capable of introducing, with high efficiency, a hydrolyzable silyl group having a desired structure corresponding to the structure of a hydrosilane compound to a polyoxyalkylene-based polymer having a high molecular weight, and capable of reducing the amount of Si-H groups included in the polyoxyalkylene-based polymer having a hydrolyzable silyl group; a polyoxyalkylene-based polymer obtained by the method; a curable composition comprising the polyoxyalkylene-based polymer; and a cured product of the curable composition.　The present invention produces a polyoxyalkylene-based polymer by the method involving: carrying out hydrosilylation of a polyoxyalkylene-based polymer (B) having an allyl group and a hydrosilane compound (C) in the presence of a hydrosilylation reaction catalyst (D) to produce a polyoxyalkylene-based polymer (A1) having a hydrolyzable silyl group; and reacting the polyoxyalkylene-based polymer (A1) with a hydroxy group-containing compound (E) to produce a polyoxyalkylene-based polymer (A) having a number average molecular weight of more than 3,000.

Description

Method for producing polyoxyalkylene polymer, polyoxyalkylene polymer, and curable composition

[0001] The present invention relates to a method for producing a polyoxyalkylene polymer, a polyoxyalkylene polymer that can be produced by the method, 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 is often used as a catalyst for the hydrosilylation reaction. However, when a Karstedt catalyst is used, side reactions such as internal isomerization and hydrogenation occur in some cases, making it difficult to efficiently introduce a hydrolyzable silyl group having a structure corresponding to that of the hydrosilane compound into the organic polymer.

[0004] As a method capable of suppressing side reactions when using a Karstedt catalyst, for example, a method of carrying out hydrosilylation using a specific ruthenium catalyst has been proposed (see Patent Document 1).

[0005] Japanese Patent Application Laid-Open No. 2021-11456

[0006] As described in Patent Document 1, when a compound having an allyl group is reacted with a hydrosilane compound, the use of a metal catalyst containing a metal other than platinum as a hydrosilylation reaction catalyst may allow for more efficient introduction of a hydrolyzable silyl group having a structure corresponding to that of the hydrosilane compound than when a Karstedt catalyst is used. On the other hand, the method described in Patent Document 1 tends to result in a lower introduction rate of the hydrolyzable silyl group when producing an organosilicon compound having a molecular weight of more than 3,000. For this reason, a more preferable catalyst system is desired.

[0007] Furthermore, when attempting to introduce a hydrolyzable silyl group having a structure corresponding to that of a hydrosilane compound into an organosilicon compound with high efficiency by a hydrosilylation reaction in which the hydrosilane compound is reacted with an allyl group, a method using a molar excess of the hydrosilane compound relative to the allyl group is advantageous from the viewpoints of reactivity and selectivity. However, this method has the problem that a portion of the hydrosilane compound is susceptible to disproportionation reaction and condensation between hydrosilane compounds due to the action of the metal catalyst, thereby modifying the hydrosilane compound to a hydrosilane compound having multiple Si—H groups per molecule.

[0008] When the boiling point of a hydrosilane compound having multiple Si—H groups per molecule, which is produced by modifying a hydrosilane compound, is higher than the boiling point of the hydrosilane compound before modification, it is difficult to remove the hydrosilane compound having multiple Si—H groups by devolatilization under reduced pressure. Thus, the high-boiling hydrosilane compound having multiple Si—H groups is likely to remain in the organic polymer having a hydrolyzable silyl group.

[0009] Furthermore, when a hydrosilane compound having multiple Si—H groups per molecule reacts with an allyl group bonded to an organic polymer, the rate of incorporation of hydrolyzable silyl groups having a target structure corresponding to the structure of the hydrosilane compound before modification into the organic polymer decreases, and the Si—H groups are retained on the hydrolyzable silyl groups in the resulting organic polymer having hydrolyzable silyl groups. In this case, there is a problem that removal of the Si—H groups by devolatilization under reduced pressure becomes even more difficult.

[0010] Furthermore, when an Si—H group possessed by the organic polymer or an Si—H group possessed by a compound contained in the organic polymer remains in an organic polymer having a hydrolyzable silyl group, problems arise such that hydrogen gas is generated during storage of the organic polymer or a curable composition containing the organic polymer, making the storage container prone to expansion, and bubbles are generated during curing of the curable composition, making the appearance of the cured product prone to be impaired.

[0011] In view of the above circumstances, there is a need for a method that can highly efficiently introduce hydrolyzable silyl groups having a structure corresponding to that of a hydrosilane compound into a high-molecular-weight organosilicon compound, that can reduce the amount of Si—H groups contained in a polyoxyalkylene polymer having a hydrolyzable silyl group, and that can thereby suppress expansion of a storage container during storage of a polyoxyalkylene polymer having a hydrolyzable silyl group or a curable composition containing a polyoxyalkylene polymer having a hydrolyzable silyl group, and that can suppress the generation of bubbles during curing of the curable composition.

[0012] Therefore, an object of the present invention is to provide a method for producing a polyoxyalkylene polymer, which method enables highly efficient introduction of a hydrolyzable silyl group of a desired structure corresponding to the structure of a hydrosilane compound into a high-molecular-weight polyoxyalkylene polymer and enables a reduction in the amount of Si—H groups contained in the polyoxyalkylene polymer having a hydrolyzable silyl group; a polyoxyalkylene polymer obtained by the method; a curable composition containing the polyoxyalkylene polymer; and a cured product of the curable composition.

[0013] As a result of intensive investigations into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a method comprising: carrying out hydrosilylation of an allyl group-containing polyoxyalkylene polymer (B) with a hydrosilane compound (C) in the presence of a hydrosilylation catalyst (D) to produce a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1); and reacting the polyoxyalkylene polymer (A1) with a hydroxyl group-containing compound (E) to produce a polyoxyalkylene polymer (A) having a number average molecular weight of more than 3,000, thereby completing the present invention.

[0014] That is, the present invention provides a method for producing a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group by hydrosilylation of a polyoxyalkylene polymer (B) having an allyl group with a hydrosilane compound (C), and reacting the polyoxyalkylene polymer (A1) with a hydroxyl group-containing compound (E) to produce a polyoxyalkylene polymer (A), wherein the polyoxyalkylene polymer (A) has a number average molecular weight of more than 3,000, the hydrosilylation is carried out in the presence of a hydrosilylation catalyst (D), and the polyoxyalkylene polymer (A1) is a compound 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 from 1 to 20 carbon atoms, and a is 0, 1, or 2. The present invention relates to a method for producing a polyoxyalkylene polymer, wherein the polyoxyalkylene polymer (A1) has a Si—H group or contains a compound having a Si—H group.

[0015] The present invention also provides a polyoxyalkylene polymer having a hydrolyzable silyl group, wherein 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 may have a hydrolyzable silyl group (a1) represented by the following formula (1) and may have a Si—H group; and in the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of Si—H groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is １ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N １ ｔ is 0.85 or more and 1.00 or less, and N １ｔ The number of Si—H groups, N Ｓｉ－Ｈ The ratio of N Ｓｉ－Ｈ / N １ ｔ The polyoxyalkylene polymer has a molecular weight of 0.00 or more and less than 0.05.

[0016] The present invention provides a method for producing a polyoxyalkylene polymer, which can highly efficiently introduce a hydrolyzable silyl group of a desired structure corresponding to the structure of a hydrosilane compound into a high-molecular-weight polyoxyalkylene polymer and can reduce the amount of Si—H groups contained in the polyoxyalkylene polymer having a hydrolyzable silyl group; a polyoxyalkylene polymer obtained by the method; a curable composition containing the polyoxyalkylene polymer; and a cured product of the curable composition.

[0017] The present invention will be described in detail below.

[0018] <<Method for Producing Polyoxyalkylene Polymer>> The method for producing a polyoxyalkylene polymer includes: generating a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group by hydrosilylation of a polyoxyalkylene polymer (B) having an allyl group with a hydrosilane compound (C); and reacting the polyoxyalkylene polymer (A1) with a hydroxyl group-containing compound (E) to generate a polyoxyalkylene polymer (A). The polyoxyalkylene polymer (A) has a number-average molecular weight of more than 3,000. The hydrosilylation is carried out in the presence of a hydrosilylation catalyst (D). The polyoxyalkylene polymer (A1) has a hydrolyzable silyl group (a1) represented by the following formula (1): (1) In formula (1), R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ２ represents a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and a represents 0, 1, or 2. The polyoxyalkylene polymer (A1) has an Si—H group or contains a compound having an Si—H group.

[0019] According to the above method, by using the hydrosilylation catalyst (D), a hydrolyzable silyl group having a structure corresponding to that of the hydrosilane compound (C) can be introduced into an allyl group in the polyoxyalkylene polymer (B) with high efficiency. Furthermore, the hydrosilylation produces a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group (a1) represented by the above formula (1) that does not contain a silicon-bonded hydrogen atom. The produced polyoxyalkylene polymer (A1) may have a Si—H group or may contain a compound having a Si—H group. When the polyoxyalkylene polymer (A1) contains a compound having a Si—H group, such a compound is typically contained as an impurity in the polyoxyalkylene polymer (A1). When the Si—H group is contained in a hydrolyzable silyl group contained in a polyoxyalkylene polymer molecule, the hydrolyzable silyl group containing the Si—H group is referred to as a hydrolyzable silyl group (a2-1).

[0020] However, by reacting the polyoxyalkylene polymer (A1) which has the hydrolyzable silyl group (a1) generated by hydrosilylation and also has an Si—H group or a compound having an Si—H group, with the hydroxyl group-containing compound (E), the hydrogen atom of the Si—H group is converted to an organoxy group derived from the hydroxyl group-containing compound (E).

[0021] Furthermore, when the hydrolyzable silyl group (a2-1) containing a Si—H group is represented by the following formula (2), the hydrolyzable silyl group represented by formula (2) will be referred to as a hydrolyzable silyl group (a2-2). (2) In formula (2), 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. When the hydrolyzable silyl group (a2-2) is converted to the hydrolyzable silyl group (a1), the amount of the hydrolyzable silyl group (a2-2) decreases and the amount of the hydrolyzable silyl group (a1) increases. The concept of the hydrolyzable silyl group (a2-2) is included in the concept of the hydrolyzable silyl group (a2-1) containing a Si—H group.

[0022] The polyoxyalkylene polymer (A) obtained by the above method has only a small amount of Si—H groups in the molecule or no Si—H groups at all, and also contains only a small amount of compounds having Si—H groups or no Si—H groups at all.

[0023] As a result, swelling of a storage container due to generation of hydrogen gas during storage of the polyoxyalkylene polymer (A) or a curable composition containing the polyoxyalkylene polymer (A) and generation of bubbles due to generation of hydrogen gas during curing of the curable composition containing the polyoxyalkylene polymer (A) are suppressed. The generation of hydrogen gas is caused by Si—H groups.

[0024] As described above, the number-average molecular weight of the finally obtained polyoxyalkylene polymer (A) is more than 3,000. Here, the number-average molecular weight is the polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). A cured product obtained from a polyoxyalkylene polymer (A) having such a molecular weight exhibits good mechanical properties such as high tensile strength at break and high tensile elongation at break. Therefore, a curable composition containing the polyoxyalkylene polymer (A) can be suitably used as an adhesive, a sealant, an elastic coating agent, a pressure-sensitive adhesive, etc.

[0025] The number average molecular weight of the polyoxyalkylene polymer (A) 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 (A). The number average molecular weight of the polyoxyalkylene polymer (A) 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 (A) and the curable composition containing the polyoxyalkylene polymer (A), the number average molecular weight of the polyoxyalkylene polymer (A) 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.

[0026] The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polyoxyalkylene polymer (A) 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.

[0027] The method for producing the polyoxyalkylene polymer (A) will be described in detail below.

[0028] <Production of Polyoxyalkylene Polymer (A1)> In the above method, first, a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group is produced by hydrosilylation of a polyoxyalkylene polymer (B) having an allyl group with a hydrosilane compound (C). The bonding position of the allyl group in the polyoxyalkylene polymer (B) is not particularly limited, but is typically a terminal of the molecular chain. When the bonding position of the allyl group in the polyoxyalkylene polymer (B) is a terminal of the molecular chain, the bonding position of the hydrolyzable silyl group in the polyoxyalkylene polymer (A1) is also a terminal of the molecular chain.

[0029] The allyl group-containing polyoxyalkylene polymer (B) has a polyoxyalkylene skeleton, which is preferably 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.

[0030] 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.

[0031] The molecular chain structure of the polyoxyalkylene polymer (B) may be linear or branched. When the molecular chain structure of the polyoxyalkylene polymer (B) is linear, the molecular chain structure of the polyoxyalkylene polymer (A1) derived from the polyoxyalkylene polymer (B) and the molecular chain structure of the polyoxyalkylene polymer (A) described below are also linear. When the molecular chain structure of the polyoxyalkylene polymer (B) is branched, the molecular chain structure of the polyoxyalkylene polymer (A1) derived from the polyoxyalkylene polymer (B) and the molecular chain structure of the polyoxyalkylene polymer (A) described below are also branched.

[0032] The polyoxyalkylene polymer (B) may contain linear molecules and branched molecules.

[0033] A linear molecule is preferred in that the cured product of the curable composition containing the polyoxyalkylene polymer (A) described below has good elongation, whereas a branched molecule is preferred in that the curable composition of the polyoxyalkylene polymer (A) described below has good strength.

[0034] 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.

[0035] 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 (B) may contain only molecules having one type of polyoxyalkylene skeleton, or may contain multiple types of molecules having different types of polyoxyalkylene skeletons.

[0036] When the curable composition containing the polyoxyalkylene polymer (A) obtained by the above method is used as a sealant, adhesive, etc., the mass ratio of oxypropylene repeating units to the mass of the polyoxyalkylene skeleton in the polyoxyalkylene polymer (B), the polyoxyalkylene polymer (A1), and the polyoxyalkylene polymer (A) is preferably 50 mass% or more, more preferably 80 mass% or more. In this case, the polyoxyalkylene polymer (A) is amorphous. Furthermore, the viscosity of the polyoxyalkylene polymer (A) tends to be low.

[0037] The polyoxyalkylene skeleton of the polyoxyalkylene polymer (B) can be formed by a conventionally known method, by ring-opening polymerization of a cyclic ether compound in the presence of an initiator using a polymerization catalyst, to obtain a polyoxyalkylene polymer (B1) having a hydroxyl group.

[0038] Examples of methods for producing the polyoxyalkylene polymer (B1) 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 a zinc hexacyanocobaltate glyme complex is preferred, as it is easy to obtain a polyoxyalkylene polymer (B1) having a narrow molecular weight distribution (Mw / Mn).

[0039] 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 (B1).

[0040] 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.

[0041] 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.

[0042] In order to introduce allyl groups into the hydroxyl groups of the polyoxyalkylene polymer (B1), an alkali metal compound is reacted with the hydroxyl groups 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.

[0043] 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.

[0044] The amount of the alkali metal compound used is not particularly limited as long as it can introduce a desired amount of allyl groups into the hydroxyl groups of the polyoxyalkylene polymer (B1). 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 (B1). 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 (B1). 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, particularly preferably 0.8 mol or more to 1.1 mol or less, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer (B1).

[0045] In order to ensure that the reaction between the hydroxyl groups of the polyoxyalkylene polymer (B1) and the alkali metal compound proceeds smoothly, it is preferable to remove water and alcohol other than the polyoxyalkylene polymer (B1) from the reaction solution containing the polyoxyalkylene polymer (B1) 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.

[0046] The temperature at which the hydroxyl groups of the polyoxyalkylene polymer (B1) 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 (B1) 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.

[0047] The polyoxyalkylene polymer (B2) whose hydroxyl groups have been converted to alkali metal alcoholates as described above is reacted with an allyl halide to obtain a polyoxyalkylene polymer (B) having allyl groups.

[0048] 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.

[0049] 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 (B2). 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 (B1) used to prepare the polyoxyalkylene polymer (B2). 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 (B1) used to prepare the polyoxyalkylene polymer (B2). 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 (B1) used to prepare the polyoxyalkylene polymer (B2).

[0050] The reaction temperature of the polyoxyalkylene polymer (B2) with the allyl halide is preferably 50° C. or more and 150° C. or less, more preferably 110° C. or more and 140° C. or less. The reaction time of the polyoxyalkylene polymer (B2) with the allyl halide is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

[0051] The polyoxyalkylene polymer (B) having an allyl group obtained as described above is subjected to hydrosilylation with a hydrosilane compound (C) to produce a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group. The hydrosilylation is carried out in the presence of a hydrosilylation catalyst (D).

[0052] The polyoxyalkylene polymer (A1) has a hydrolyzable silyl group (a1) represented by the following formula (1). (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.

[0053] The polyoxyalkylene polymer (A1) 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.

[0054] For this reason, a compound represented by the following formula (1-1) is used as the hydrosilane compound (C): 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 (C) represented by formula (1-1) undergoes a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer (B) to give a hydrolyzable silyl group (a1) represented by formula (1).

[0055] The polyoxyalkylene polymer (A1) has a Si—H group or contains a compound having a Si—H group. That is, the Si—H group may be contained in the polymer molecule, or a hydrosilane compound molecule contained in the polymer as an impurity may have the Si—H group. When the polyoxyalkylene polymer (A1) contains a Si—H group in the molecule, the hydrolyzable silyl group containing the Si—H group is referred to as a hydrolyzable silyl group (a2-1).

[0056] The structure of the hydrolyzable silyl group (a2-1) is not particularly limited. A preferred example of the structure of the hydrolyzable silyl group (a2-1) is a structure represented by the following formula (3). (3) In formula (3), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as those in a. n is an integer of 0 or more. The hydrolyzable silyl group represented by formula (3) is produced by a hydrosilylation reaction between a hydrosilane compound represented by formula (4) described later and an allyl group contained in the polyoxyalkylene polymer (B). There is no particular upper limit for n, and n is usually 10 or less.

[0057] A typical example of the hydrolyzable silyl group (a2-1) containing an Si—H group is a hydrolyzable silyl group (a2-2) represented by the following formula (2): The hydrosilane compound (C) may undergo a disproportionation reaction to be modified into a hydrosilane compound having multiple Si—H groups per molecule. The hydrosilane compound having multiple Si—H groups per molecule produced by the modification reacts with an allyl group in the allyl-containing polyoxyalkylene polymer (B), thereby producing the hydrolyzable silyl group (a2-2) represented by the following formula (2): (2) In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２ , and a are the same. b is 1 or 2. a+b is 1 or more and 3 or less.

[0058] When the polyoxyalkylene polymer (A1) contains a compound having an Si—H group as an impurity, the molecular structure of the compound having an Si—H group is not particularly limited. A typical structure of the compound having an Si—H group is a structure 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 a. n is an integer of 0 or more. A compound having a structure represented by formula (4) is produced by condensation of two or more molecules of the hydrosilane compound (C) in a reaction system. The upper limit of n is not particularly limited, but is usually 10 or less. The Si—H group in the polyoxyalkylene polymer (A1) and the Si—H group in the hydrosilane compound represented by formula (4) are difficult to remove by devolatilization under reduced pressure.

[0059] Furthermore, the polyoxyalkylene polymer (A1), which is a product of the hydrosilylation reaction, 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 an allyl group as a side reaction. The propyl group can be produced by a hydrogenation reaction of an allyl group as a side reaction. The above method suppresses the remaining unreacted allyl group in the polyoxyalkylene polymer (A1), and the side reaction of internal isomerization or hydrogenation.

[0060] In the above formula (1) and formula (2), the oxygen atom bonded to the propane-1,3-diyl group is bonded to any position in the polyoxyalkylene skeleton of the polyoxyalkylene polymer (A1). 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.

[0061] In formula (1) and formula (2), R １ , and R ２R 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.

[0062] R １ , and R ２ When 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.

[0063] R １ , and R ２Specific 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.

[0064] 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.

[0065] In formula (1) and formula (2), a is 0, 1, or 2. In terms of curability, a is preferably 0 or 1. Furthermore, in formula (2), 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.

[0066] In the group represented by formula (1), —SiR １ ａ (OR ２ ) ３－ａ Preferred 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.

[0067] 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.

[0068] In addition, in the group represented by formula (2), —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 (2) is a group substituted with a hydrogen atom. １ ａ H ｂ (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 (OCH２ 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.

[0069] Specific examples of the hydrosilane compound (C) 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.

[0070] In terms of the curability of the polyoxyalkylene polymer (A) to be finally obtained and the strength of the cured product of the curable composition containing the polyoxyalkylene polymer (A), trimethoxysilane and dimethoxymethylsilane are particularly preferred as the hydrosilane compound (C).

[0071] 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 (B). 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 (B). 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). When the hydrosilane compound (C) is used in an amount within the above range, side reactions are suppressed, the desired hydrolyzable silyl groups can be introduced more efficiently, and a polyoxyalkylene polymer (A) that has a low viscosity and is easy to handle is easily obtained.

[0072] The hydrosilylation reaction described above is carried out in the presence of a hydrosilylation catalyst (D). The hydrosilylation catalyst (D) is not particularly limited, and examples thereof include metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, as well as complexes of the aforementioned metals. In particular, carrying out the hydrosilylation reaction in the presence of a ruthenium complex (D1) makes it easier to obtain a polyoxyalkylene polymer (A1) having a high content of hydrolyzable silyl groups. The ruthenium complex (D1) is not particularly limited, as long as it is a complex containing a ruthenium atom and is a complex compound that effectively promotes the hydrosilylation reaction.

[0073] The ruthenium complex (D1) is preferably a complex compound having a ligand (F1) derived from compound (F). Compound (F) has at least one carbon-carbon double bond and at least one electron-withdrawing group per molecule. Here, the carbon-carbon double bond possessed by compound (F) may be an ethylenic carbon-carbon double bond or an aromatic carbon-carbon double bond. Furthermore, in compound (F), at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.

[0074] The ruthenium complex (D1) may have one or more types of ligand (F1).

[0075] Examples of the electron-withdrawing group contained in compound (F) 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 (F) 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.

[0076] 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 (F) 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 (F) preferably has one or more electron-withdrawing groups selected from a bromo group and an iodo group per molecule. In this case, compound (F) 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 (F).

[0077] Compound (F) 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 a bridged aliphatic cyclic skeleton, 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 (F) 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.

[0078] Specific preferred examples of compound (F) 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.

[0079] 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 (F) in terms of high selectivity for conversion of an allyl group to a hydrolyzable silyl group (a1).

[0080] The ruthenium complex (D1) can be produced by a known production method. Examples of raw materials for the ruthenium complex (D1) include anhydrides and hydrates of compounds selected from ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. For example, the ruthenium complex (D1) can be specifically produced by the following production method. First, compound (F) 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 the ruthenium complex (D1). 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 in order to neutralize hydrogen chloride generated during heating under reflux. When ruthenium (III) chloride hydrate is reacted with compound (F), it is preferable to use compound (F) in an amount of 1 molar equivalent or more relative to the starting ruthenium compound, from the viewpoint of the reaction rate.

[0081] The ruthenium complex (D1) may be a nanoparticle catalyst. The particle size (cumulative median diameter) of the nanoparticles of the ruthenium complex (D1) 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 (D1) 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).

[0082] The ruthenium complex (D1) may contain, in addition to the ligand (F1) derived from the compound (F), a ligand (F'1) derived from a compound (F') that does not fall under the category of the compound (F). The compound (F') is a compound that can coordinate to a ruthenium atom and does not fall under the category of the compound (F). Specific examples of the ligand (F'1) derived from the compound (F') 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.

[0083] When the ruthenium complex (D1) has both a ligand (F1) derived from compound (F) and a ligand (F'1) derived from compound (F'), a higher proportion of the ligand (F1) derived from compound (F) among all the ligands contained in the ruthenium complex (D1) is preferable because this allows for higher selectivity in converting an allyl group to a hydrolyzable silyl group (a1) in the hydrosilylation reaction. The ratio of the number of ligands (F1) derived from compound (F) to the total number of ligands contained in the ruthenium complex (D1) may be 1 mol % or more and 100 mol % or less, preferably 50 mol % or more and 100 mol % or less, more preferably 70 mol % or more and 100 mol % or less, and even more preferably 90 mol % or more and 100 mol % or less.

[0084] In the hydrosilylation reaction, a ruthenium compound (D'1) that does not have a ligand (F1) derived from compound (F) may be reacted with compound (F) in a reaction solution to produce a ruthenium complex (D1). Specific examples of the ruthenium compound (D'1) include ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. Furthermore, the ruthenium compound (D'1) may be a ruthenium complex that does not have a ligand (F1) but has a ligand (F'1).

[0085] The amount of the ruthenium complex (D1) 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 (B). The amount of the ruthenium complex (D1) 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 (B). The amount of the ruthenium complex (D1) 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 polyoxyalkylene polymer (B) having an allyl group. When the amount of the ruthenium complex (D1) used is within the above range, the allyl groups in the polyoxyalkylene polymer (B) can be converted to hydrolyzable silyl groups (a1) with high efficiency.

[0086] 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.

[0087] 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, 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.

[0088] 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.

[0089] The hydrosilylation reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

[0090] The hydrosilylation is also preferably carried out in the presence of the compound (F). That is, the hydrosilylation is preferably carried out in the presence of the ruthenium complex (D1) and the compound (F). In this case, the allyl groups in the polyoxyalkylene polymer (B) are easily converted to hydrolyzable silyl groups (a1) with high efficiency.

[0091] <Production of Polyoxyalkylene Polymer (A)> The polyoxyalkylene polymer (A1) produced via the hydrosilylation reaction as described above is then reacted with a hydroxyl group-containing compound (E) to produce the polyoxyalkylene polymer (A). As described above, the polyoxyalkylene polymer (A1) has a hydrolyzable silyl group (a1). The polyoxyalkylene polymer (A1) also has a Si—H group or contains a compound having a Si—H group. By reacting the polyoxyalkylene polymer (A1) with the hydroxyl group-containing compound (E), hydrogen atoms in the Si—H groups of the polyoxyalkylene polymer (A1) or the Si—H groups of the compounds contained in the polyoxyalkylene polymer (A1) are substituted with organoxy groups derived from the hydroxyl group-containing compound (E). When the hydrolyzable silyl group (a2-1) containing a Si—H group is the hydrolyzable silyl group (a2-2) represented by the above formula (2), the hydrolyzable silyl group (a2-2) in the polyoxyalkylene polymer (A1) is converted into the hydrolyzable silyl group (a1) by reacting the polyoxyalkylene polymer (A1) with the hydroxyl group-containing compound (E) in this manner.

[0092] The hydroxyl group-containing compound (E) is not particularly limited as long as it is a hydroxyl group-containing compound that reacts with the polyoxyalkylene polymer (A1) to produce the polyoxyalkylene polymer (A). Suitable examples of the hydroxyl group-containing compound (E) include alcohol compounds, phenol compounds, oxime compounds, and carboxylic acid compounds. Among these, alcohol compounds are most preferred. For convenience, in the specification of the present application, carboxylic acid compounds are defined as being included in the hydroxyl group-containing compound.

[0093] The molecular weight of the hydroxyl group-containing compound (E) is not particularly limited. After the hydroxyl group-containing compound (E) and the polyoxyalkylene polymer (A1) are reacted to produce the polyoxyalkylene polymer (A), the hydroxyl group-containing compound (E) is preferably removed. For this reason, the molecular weight of the hydroxyl group-containing compound (E) is preferably low. A low-molecular-weight hydroxyl group-containing compound (E) is easily removed by devolatilization under reduced pressure. The molecular weight of the hydroxyl group-containing compound (E) may be 1,000 or less, preferably 500 or less, more preferably 200 or less, and even more preferably 100 or less.

[0094] As the hydroxyl group-containing compound (E), for example, a hydroxyl group-containing compound represented by the following formula can be used: R ３ (OH) ｍ In the above formula, R ３ is an m-valent organic group, where m is an integer of 1 or more. ３ is an m-valent organic group. When m is 1, examples of the monovalent organic group include a monovalent chain aliphatic hydrocarbon group and a monovalent cyclic aliphatic hydrocarbon group.

[0095] The monovalent chain aliphatic hydrocarbon group may be linear or branched. ３ Specific examples of the monovalent chain aliphatic hydrocarbon group as include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1,1-dimethylethyl group, a 2,2-dimethylethyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, an ethenyl group (a vinyl group), a 1-propenyl group, a 2-propenyl group (an allyl group), a butenyl group, a hexenyl group, an octenyl group, a decenyl group, an ethynyl group, a propynyl group, a butynyl group, a hexynyl group, an octynyl group, and a pentadecynyl group. The monovalent chain aliphatic hydrocarbon group may be a group having a molecular weight greater than that of these groups.

[0096] The monovalent cycloaliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. ３Specific examples of the monovalent alicyclic hydrocarbon group as include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentadienyl group, a cyclohexenyl group, and a cyclobutynyl group. The monovalent alicyclic hydrocarbon group may be a group having a molecular weight greater than that of these groups.

[0097] R ３ The m-valent organic group may have a substituent. Examples of the substituent include an alkoxy group and a halogeno group. The number of the substituent is not particularly limited. In addition, the organic group may have one or more methylene groups (-CH ２ When a methylene group in the organic group is contained, the methylene group in the organic group may be replaced with an ether bond (—O—), a thioether bond (—S—), or a carbonyl group (—C(═O)—).

[0098] In the above formula, when m is an integer of 2 or more, the monovalent organic group, including the examples, is interpreted as an m-valent organic group. For example, when m is 2, the alkyl group is interpreted as an alkanediyl group. When m is 3, the alkyl group is interpreted as an alkanetriyl group.

[0099] When m is 2, specific examples of the alcohol compound represented by the above formula include glycol compounds such as 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol (trimethylene glycol), 1,4-butanediol (tetramethylene glycol), diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polycarbonate diol; dihydroxybenzene compounds such as catechol and resorcinol; dihydroxyheteroaryl compounds such as 4,6-dihydroxy-2-methylpyrimidine and 3,6-dihydroxy-4-methylpyridazine; bisphenol compounds such as bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, and bisphenol Z; and sugar alcohol dehydrates such as isosorbide and isomannide.

[0100] When m is 3, a specific example of the alcohol compound represented by the above formula includes glycerin. The alcohol compound may be any of a primary alcohol, a secondary alcohol, and a tertiary alcohol. From the viewpoint of good curability of the polyoxyalkylene polymer (A), the alcohol compound is preferably a primary alcohol or a secondary alcohol, and more preferably a primary alcohol. Among the primary alcohols, methanol and ethanol are preferred, and methanol is more preferred.

[0101] In addition, from the viewpoint of good curability of the polyoxyalkylene polymer (A), the alcohol compound is preferably propargyl alcohol or hydroxyacetone, and more preferably hydroxyacetone.

[0102] When the hydroxyl group-containing compound (E) is a phenol compound, R ３may be a monovalent aromatic hydrocarbon group having 6 or more carbon atoms. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, an indenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthryl group, and phenyl is more preferred. When the monovalent aromatic hydrocarbon group is a phenyl group, the hydroxyl group-containing compound (E) is a phenol.

[0103] The oxime compound is not particularly limited as long as it has a structure represented by >C=N—OH. Examples of the carboxylic acid compound include formic acid, oxalic acid, acetic acid, lactic acid, propionic acid, butyric acid, lauric acid, tridecylic acid, palmitic acid, stearic acid, and ascorbic acid.

[0104] There is no particular upper limit for m. m is usually preferably an integer of 1 or more and 5 or less, more preferably 1 or 2, and most preferably 1. When m is 1, crosslinking of polymer molecules due to reaction of hydroxyl groups of the alcohol compound with Si—H groups on two or more polymer molecules does not occur. When crosslinking of polymer molecules occurs, the molecular weight of the polymer increases, and the viscosity of the polyoxyalkylene polymer (A) may increase.

[0105] The hydroxyl group-containing compound (E) may be used alone or in combination of two or more kinds.

[0106] The reaction of the Si—H groups of the polyoxyalkylene polymer (A1) and the Si—H groups of the compounds contained in the polyoxyalkylene polymer (A1) with the hydroxyl group-containing compound (E) can proceed in the presence of the hydrosilylation catalyst (D) already present in the reaction system, but a new hydrosilylation catalyst (D) may also be added. The type of catalyst is not particularly limited, and conventionally known hydrosilylation catalysts such as metals such as cobalt, nickel, manganese, iridium, platinum, palladium, and rhodium; and complexes of these metals can be used. Specific examples of suitable catalysts include catalysts in which platinum is supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and an alcohol, aldehyde, ketone, or the like; platinum-olefin complexes [e.g., Pt(CH ２ =CH２ ) ２ (PPh ３ ), Pt(CH ２ =CH ２ ) ２ Cl ２ platinum divinyldisiloxane complexes [e.g., Pt{(vinyl)Me ２ SiOSiMe ２ (vinyl)}, Pt{Me(vinyl)SiO} ４ platinum-phosphine complexes [e.g., Ph(PPh ３ ) ４ , Pt(PBu ３ ) ４ ]; platinum-phosphite complexes [e.g., Pt{P(OPh) ３} ４ From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum divinyldisiloxane complexes are preferred as the catalyst.

[0107] The amount of the catalyst used is preferably from 1 ppm by mass to 1000 ppm by mass, more preferably from 5 ppm by mass to 800 ppm by mass, and even more preferably from 10 ppm by mass to 500 ppm by mass, relative to the mass of the polyoxyalkylene polymer (A1).

[0108] The amount of the hydroxyl group-containing compound (E) used is not particularly limited. The amount of the hydroxyl group-containing compound (E) used may be appropriately determined depending on the sum of the amount of Si—H groups in the polyoxyalkylene polymer (A1) and the amount of Si—H groups derived from the compound containing the Si—H group contained in the polyoxyalkylene polymer (A1). The amount of the hydroxyl group-containing compound (E) used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the polyoxyalkylene polymer (A1). The upper limit of the amount of the hydroxyl group-containing compound (E) used is not particularly limited. The amount of the hydroxyl group-containing compound (E) used may be, for example, 100 parts by mass or less, 50 parts by mass or less, or 10 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A1). The amount of the hydroxyl group-containing compound (E) used may be 0.1 to 100 parts by mass, 0.5 to 50 parts by mass, or 1 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A1). Usually, after completion of the reaction, unreacted hydroxyl group-containing compound (E) is distilled off from the resulting polyoxyalkylene polymer (A). Therefore, the amount of the hydroxyl group-containing compound (E) used is preferably a small amount, such as 0.1 to 10 parts by mass, or 0.1 to 5 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A1).

[0109] The reaction of the Si—H groups of the polyoxyalkylene polymer (A1) and the Si—H groups derived from the compound containing the Si—H group contained in the polyoxyalkylene polymer (A1) with the hydroxyl group-containing compound (E) may be carried out in the presence or absence of a solvent. Usually, after completion of the reaction, the solvent is distilled off from the polyoxyalkylene polymer (A). Therefore, the reaction is preferably carried out in the absence of a solvent. Specific examples of suitable solvents include hydrocarbon solvents such as hexane, and halogenated hydrocarbon solvents such as dichloromethane.

[0110] The reaction temperature between the Si—H groups of the polyoxyalkylene polymer (A1) and the Si—H groups derived from the compound containing the Si—H group contained in the polyoxyalkylene polymer (A1) and the hydroxyl group-containing compound (E) is not particularly limited as long as the reaction proceeds to a desired extent. The reaction temperature is, for example, preferably from 0° C. to 150° C., more preferably from 30° C. to 120° C., and even more preferably from 50° C. to 100° C.

[0111] As described above, the polyoxyalkylene polymer (A1) is reacted with the hydroxyl group-containing compound (E) to produce the polyoxyalkylene polymer (A). Then, if necessary, volatile components are distilled off from the polyoxyalkylene polymer (A), thereby obtaining the polyoxyalkylene polymer (A).

[0112] As described above, the above method makes it possible to obtain a polyoxyalkylene polymer (A) which does not contain, or contains only a small amount of, the Si—H group contained in the polyoxyalkylene polymer (A1) and the Si—H group derived from the compound having the Si—H group contained in the polyoxyalkylene polymer (A1).

[0113] As a result, swelling of a storage container due to the generation of hydrogen gas during storage of the polyoxyalkylene polymer (A) or a curable composition containing the polyoxyalkylene polymer (A) and the generation of bubbles due to the generation of hydrogen gas during curing of the curable composition containing the polyoxyalkylene polymer (A) are suppressed. The generation of hydrogen gas is caused by Si-H groups.

[0114] In the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of Si—H groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is １ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N １ ｔIn the polyoxyalkylene polymer, the total N of the number of hydrolyzable silyl groups (a1), the number of hydrolyzable silyl groups (a2-1) containing a Si—H group, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is preferably 0.85 or more and 1.00 or less, more preferably 0.90 or more and 1.00 or less, and even more preferably 0.95 or more and 1.00 or less. ２ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ２ ｔ In the polyoxyalkylene polymer, the total N of the number of hydrolyzable silyl groups (a1), the number of hydrolyzable silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is preferably 0.85 or more and 1.00 or less, more preferably 0.90 or more and 1.00 or less, and even more preferably 0.95 or more and 1.00 or less. ３ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ３ ｔ is preferably 0.85 or more and 1.00 or less, more preferably 0.90 or more and 1.00 or less, and even more preferably 0.95 or more and 1.00 or less.

[0115] Also, N １ ｔ The number of Si—H groups, N Ｓｉ－Ｈ The ratio of N Ｓｉ－Ｈ / N １ ｔ is preferably 0.00 or more and less than 0.05, more preferably 0.00 or more and 0.10 or less, and even more preferably 0.00 or more and 0.05 or less. ２ ｔ The number N of hydrolyzable silyl groups (a2-1) containing Si—H groups relative to ａ２－１ The ratio of N ａ２－１ / N ２ ｔis preferably 0.00 or more and less than 0.05, more preferably 0.00 or more and 0.10 or less, and even more preferably 0.00 or more and 0.05 or less. ３ ｔ The number N of hydrolyzable silyl groups (a2-2) represented by formula (2) relative to ａ２－２ The ratio of N ａ２－２ / N ３ ｔ is preferably 0.00 or more and less than 0.05, more preferably 0.00 or more and 0.10 or less, and even more preferably 0.00 or more and 0.05 or less.

[0116] N ａ１ / N １ ｔ , N ａ１ / N ２ ｔ , N ａ１ / N ３ ｔ , N Ｓｉ－Ｈ / N ２ ｔ , and N ａ２－２ / N ３ ｔ teeth, １ The H NMR can be used to determine the ratio of the hydrolyzable silyl group (a1), the hydrolyzable silyl group (a2-2), the Si—H group, 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 Si—H group, the hydrolyzable silyl group (a2-1), the hydrolyzable silyl group (a2-2), the 1-propenyl group, the propyl group, and the allyl group are clearly distinguishable.

[0117] 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 (C), a peak derived from one proton is observed near 4.5 ppm. These peaks can be distinguished by the fact that the former is hardly reduced by removal under reduced pressure, while the latter is easily reduced or disappears by removal under reduced pressure. Furthermore, a peak derived from a 1-propenyl group is observed as multiple peaks derived from one proton 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 various ratios described above can be determined based on the integrals of these peaks.

[0118] <Curable Composition> The curable composition contains, as a polyoxyalkylene polymer, the polyoxyalkylene polymer (A) having a hydrolyzable silyl group produced by the above-described method, and also contains a curing catalyst as a component for curing the polyoxyalkylene polymer.

[0119] Components other than the polyoxyalkylene polymer that may be contained in the curable composition will be described below.

[0120] (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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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).

[0127] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] (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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] (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.

[0136] 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.

[0137] 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.

[0138] (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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] (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.

[0143] (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.

[0144] 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.

[0145] (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.

[0146] 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.

[0147] (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.

[0148] 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.

[0149] (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).

[0150] 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.

[0151] (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.

[0152] 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.

[0153] 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.

[0154] (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.

[0155] 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.

[0156] The amount of the tackifier resin used is preferably 2 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer.

[0157] (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.

[0158] (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.

[0159] 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.

[0160] (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.

[0161] 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.

[0162] (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.

[0163] 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 to epoxy resin.

[0164] 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.

[0165] 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.

[0166] The curable composition described above is cured by a method appropriate for the intended use of the curable composition to form a cured product.

[0167] <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.

[0168] 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.

[0169] <<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 can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer. 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.

[0170] 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.

[0171] That is, the present invention includes the following.

[0172] <1> A method for producing a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group by hydrosilylation of a polyoxyalkylene polymer (B) having an allyl group with a hydrosilane compound (C), and reacting the polyoxyalkylene polymer (A1) with a hydroxyl group-containing compound (E) to produce a polyoxyalkylene polymer (A), wherein the polyoxyalkylene polymer (A) has a number-average molecular weight of more than 3,000, the hydrosilylation is carried out in the presence of a hydrosilylation catalyst (D), and the polyoxyalkylene polymer (A1) is a compound 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 from 1 to 20 carbon atoms, and a is 0, 1, or 2.) and the polyoxyalkylene polymer (A1) has a Si—H group or contains a compound having a Si—H group. <2> A method for producing a polyoxyalkylene polymer according to <1>, wherein the polyoxyalkylene polymer (A1) has a hydrolyzable silyl group (a2-1) containing a Si—H group. <3> A method for producing a polyoxyalkylene polymer according to <1>, wherein the hydrolyzable silyl group (a2-1) is a group represented by the following formula (2): (2) (In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as a, b is 1 or 2, and a+b is 1 or more and 3 or less. <4> The method for producing a polyoxyalkylene polymer according to <2>, wherein the hydrolyzable silyl group (a2-2) is represented by the following formula: ３ ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ３ ｔis 0.85 or more and 1.00 or less, ３ ｔ The number N of the hydrolyzable silyl groups (a2-2) relative to ａ２－２ The ratio of N ａ２－２ / N ３ ｔ <5> The method for producing a polyoxyalkylene polymer according to <3>, wherein N is 0.00 or more and less than 0.05. ａ１ / N ３ ｔis 0.95 or more and 1.00 or less. <6> The method for producing a polyoxyalkylene polymer according to any one of <1> to <5>, wherein the hydrosilylation catalyst (D) is a ruthenium complex (D1). <7> The method for producing a polyoxyalkylene polymer according to <6>, wherein the ruthenium complex (D1) has a ligand (F1) derived from compound (F), compound (F) 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. <8> The method for producing a polyoxyalkylene polymer according to <7>, wherein compound (F) has a benzene ring skeleton or a norbornadiene skeleton. <9> The method for producing a polyoxyalkylene polymer according to <7> or <8>, wherein the compound (F) 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. <10> The method for producing a polyoxyalkylene polymer according to any one of <7> to <9>, wherein the compound (F) is at least one 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. <11> The method for producing a polyoxyalkylene polymer according to any one of <6> to <10>, wherein the hydrosilylation is carried out in the presence of a compound (F), which has at least one carbon-carbon double bond and at least one electron-withdrawing group per molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond. <12> The method for producing a polyoxyalkylene polymer according to <11>, wherein the compound (F) has a benzene ring skeleton or a norbornadiene skeleton. <13> The method for producing a polyoxyalkylene polymer according to <11> or <12>, wherein the compound (F) 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.<14> The method for producing a polyoxyalkylene polymer according to any one of <11> to <13>, wherein the compound (F) 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. <15> The method for producing a polyoxyalkylene polymer according to any one of <1> to <14>, wherein the hydrosilylation uses 3.0 moles or more of the hydrosilane compound (C) per 1.0 mole of allyl groups in the polyoxyalkylene polymer (B). <16> A polyoxyalkylene polymer having a hydrolyzable silyl group, wherein 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 may have a hydrolyzable silyl group (a1) represented by the following formula (1) and may have a Si—H group; and in the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of Si—H groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is １ ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N １ ｔ is 0.85 or more and 1.00 or less, and N １ ｔ The number N of the Si—H groups Ｓｉ－Ｈ The ratio of N Ｓｉ－Ｈ / N １ ｔ<17> The polyoxyalkylene polymer may have a hydrolyzable silyl group (a2-1) containing a Si—H group, and in the polyoxyalkylene polymer, the total N of the number of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2-1), the number of the 1-propenyl groups, the number of the propyl groups, and the number of the allyl groups is ２ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ２ ｔ is 0.85 or more and 1.00 or less, and N ２ ｔ The number N of hydrolyzable silyl groups (a2-1) relative to ａ２－１ The ratio of N ａ２－１ / N ２ ｔ <18> The polyoxyalkylene polymer according to <16>, wherein the polyoxyalkylene polymer is a compound represented by the following formula (2): (2) (In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as those in the formula (a), b is 1 or 2, and a+b is 1 or more and 3 or less.) In the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2-2), the 1-propenyl groups, the propyl groups, and the allyl groups is ３ ｔ The number N of hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ３ ｔ is 0.85 or more and 1.00 or less, and N ３ ｔ The ratio of the number of hydrolyzable silyl groups (a2) to N ａ２－２ / N ３ ｔ<19> The polyoxyalkylene polymer according to <17>, wherein N is 0.00 or more and less than 0.05. ａ１ / N １ ｔ <20> A curable composition comprising the polyoxyalkylene polymer according to any one of <16> to <19> and a curing catalyst. <21> A cured product of the curable composition according to <20>.

[0173] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0174] 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

[0175] The yield of a silyl group, a 1-propenyl group, a propyl group, an allyl group, or the like is calculated using the following nuclear magnetic resonance (NMR) apparatus: １ H NMR measurement was performed. Apparatus: AVANCE III HD500 digital instrument (manufactured by BRUKER)

[0176] Synthesis Example 1 Using polyoxypropylene glycol having a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized in the presence of 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 equivalent 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 product by distillation under reduced pressure, 1.3 mol equivalent 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 (B-1) was obtained.

[0177] Comparative Example 1: 100 ppm by mass of [RuCl] relative to the mass of polymer (B-1) ２ (nbd)] ｎ 2,3-dibromonorbornadiene was added to polymer (B-1) in an amount of 260 ppm by mass relative to the mass of polymer (B-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 has an electron-withdrawing group and is a compound capable of coordinating 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 (B-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in polymer (B-1) and dimethoxymethylsilane was carried out at 90°C. One hour after the start of the reaction, １ H NMR measurement was carried out to confirm that the allyl groups in the polymer (B-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 (A'-1). １H 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 (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total. As a result, the ratio of silyl groups (a1) represented by formula (1) was 94%, the ratio of silyl groups (a2-2) represented by formula (2) was 5%, the ratio of 1-propenyl groups was 0%, the ratio of propyl groups (hydrogenated form) was 1%, and the ratio of allyl groups was 0%.

[0178] Example 1 To 100 parts by mass of the polymer (A'-1) obtained in Comparative Example 1, 50 ppm by mass of a platinum divinyldisiloxane complex (a 3% by mass isopropanol solution in terms of platinum) relative to the mass of the polymer (A'-1) and 3 parts by mass of methanol were added. The polymer (A'-1) and methanol were reacted at 90°C for 0.5 hours, and then volatile components were distilled off under reduced pressure from the reaction solution to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (A-1). With respect to the obtained polymer (A-1), 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 (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total. As a result, the ratio of silyl groups (a1) represented by formula (1) was 99%, the ratio of silyl groups (a2-2) represented by formula (2) was 0%, the ratio of 1-propenyl groups was 0%, the ratio of propyl groups was 1%, and the ratio of allyl groups was 0%.

[0179] Comparative Example 2: 240 ppm by mass of [RuCl] relative to the mass of polymer (B-1) ２ (p-cymene)] ｎ was added to the polymer (B-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 (B-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in the polymer (B-1) and dimethoxymethylsilane was carried out at 90°C. One hour after the start of the reaction, １H NMR measurement was carried out to confirm that the allyl groups in the polymer (B-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 (A'-2). １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 88%, the proportion of silyl groups (a2-2) represented by formula (2) was 5%, the proportion of 1-propenyl groups was 5%, the proportion of propyl groups was 2%, and the proportion of allyl groups was 0%.

[0180] Example 2 To 100 parts by mass of the polymer (A'-2) obtained in Comparative Example 2, 50 ppm by mass of a platinum divinyldisiloxane complex (a 3% by mass isopropanol solution in terms of platinum) relative to the mass of the polymer (A'-2) and 3 parts by mass of methanol were added. The polymer (A'-2) and methanol were reacted at 90°C for 0.5 hours, and then volatile components were distilled off under reduced pressure from the reaction solution to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (A-2). With respect to the obtained polymer (A-2), １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 93%, the proportion of silyl groups (a2-2) represented by formula (2) was 0%, the proportion of 1-propenyl groups was 5%, the proportion of propyl groups was 2%, and the proportion of allyl groups was 0%.

[0181] Synthesis Example 2 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.

[0182] Comparative Example 3 The ruthenium complex obtained in Synthesis Example 2 was added to the polymer (B-1) in an amount of 240 ppm by mass relative to the mass of the polymer (B-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 (B-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in the polymer (B-1) and dimethoxymethylsilane was carried out at 90°C. Every hour from the start of the reaction, １ H NMR measurement was carried out, and the reaction was continued until the allyl groups in the polymer (B-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 (A'-3). １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 90%, the proportion of silyl groups (a2-2) represented by formula (2) was 8%, the proportion of 1-propenyl groups was 0%, the proportion of propyl groups was 2%, and the proportion of allyl groups was 0%.

[0183] Example 3 To 100 parts by mass of the polymer (A'-3) obtained in Comparative Example 3, 50 ppm by mass of a platinum divinyldisiloxane complex (a 3% by mass isopropanol solution calculated as platinum) relative to the mass of the polymer (A'-3) and 3 parts by mass of methanol were added. The polymer (A'-3) and methanol were reacted at 90°C for 0.5 hours, and then volatile components were distilled off under reduced pressure from the reaction solution to obtain a hydrolyzable silyl group-containing organic polymer (A-3). With respect to the obtained polymer (A-3), １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 98%, the proportion of silyl groups (a2-2) represented by formula (2) was 0%, the proportion of 1-propenyl groups was 0%, the proportion of propyl groups was 2%, and the proportion of allyl groups was 0%.

[0184] (Comparative Example 4) 240 mass ppm of [RuCl] relative to the mass of polymer (B-1) ２ (nbd)] ｎ and a chloroform solution of 1,3,5-tribromobenzene in an amount of 620 ppm by mass relative to the mass of polymer (B-1) were added to polymer (B-1). 1,3,5-Tribromobenzene 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 (B-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in polymer (B-1) and dimethoxymethylsilane was carried out at 90°C. Two hours after the start of the reaction, １ H NMR measurement was carried out to confirm that the allyl groups in the polymer (B-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 (A'-4). １H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 92%, the proportion of silyl groups (a2-2) represented by formula (2) was 5%, the proportion of 1-propenyl groups was 0%, the proportion of propyl groups was 3%, and the proportion of allyl groups was 0%.

[0185] Example 4 To 100 parts by mass of the polymer (A'-4) obtained in Comparative Example 4, 50 ppm by mass of a platinum divinyldisiloxane complex (a 3% by mass isopropanol solution in terms of platinum) relative to the mass of the polymer (A'-4) and 3 parts by mass of methanol were added. The polymer (A'-4) and methanol were reacted at 90°C for 0.5 hours, and then volatile components were distilled off under reduced pressure from the reaction solution to obtain a hydrolyzable silyl group-containing organic polymer (A-4). With respect to the obtained polymer (A-4), １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 97%, the proportion of silyl groups (a2-2) represented by formula (2) was 0%, the proportion of 1-propenyl groups was 0%, the proportion of propyl groups was 3%, and the proportion of allyl groups was 0%.

[0186] Comparative Example 5 A commercially available Karstedt catalyst (platinum divinyldisiloxane complex (3 mass % isopropanol solution in terms of platinum)) was added to the polymer (B-1) in an amount of 2,400 ppm by mass relative to the mass of the polymer (B-1), and 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in the polymer (B-1) were added to the polymer (B-1), and the hydrosilylation reaction of the polymer (B-1) with the dimethoxymethylsilane was initiated at 90°C. Every hour from the start of the reaction, １H NMR measurement was carried out, and the reaction was continued until the allyl groups in the polymer (B-1) had completely disappeared. Thereafter, volatile components were distilled off from the reaction solution under reduced pressure to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (A'-5). １ H NMR measurement was carried out to calculate the proportion of each group relative to the total number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2-2) represented by formula (2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. As a result, the proportion of silyl groups (a1) represented by formula (1) was 81%, the proportion of silyl groups (a2-2) represented by formula (2) was 0%, the proportion of 1-propenyl groups was 18%, the proportion of propyl groups was 0%, and the proportion of allyl groups was 0%.

[0187] Table 1 below shows the reaction conditions for the Examples and Comparative Examples. Table 1 also shows the ratio 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 (nbd)] ｎ Cat2: [RuCl ２ (p-cymene)] ｎ Cat 3: Ruthenium complex obtained in Synthesis Example 2 Cat 4: Commercially available Karstedt catalyst (platinum divinyldisiloxane complex (3 mass % platinum equivalent isopropanol solution)) The compounds listed in Table 1 are as follows. Com 1: 2,3-dibromonorbornadiene Com 2: 1,3,5-tribromobenzene (chloroform solution) MeOH listed in Table 1 is methanol. 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 (2).

[0188] *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%.

[0189] Table 1 shows that in Comparative Examples 1 to 5, in which hydrosilylation was performed using a ruthenium catalyst but the polyoxyalkylene polymer, the product of the hydrosilylation, was not reacted with the hydroxyl group-containing compound (E), the proportion of hydrolyzable silyl groups (a2) having a silicon-bonded hydrogen atom among the functional groups possessed by the polyoxyalkylene polymer was high. Therefore, when the polyoxyalkylene polymers obtained in Comparative Examples 1 to 5 are used, problems such as expansion of the storage container due to the generation of hydrogen atoms derived from the hydrolyzable silyl groups (a2) during storage of the polyoxyalkylene polymer or a curable composition containing the polyoxyalkylene polymer, or the generation of bubbles during curing of the curable composition containing the polyoxyalkylene polymer, which can impair the appearance of the cured product, may occur.

Claims

1. A method for producing a polyoxyalkylene polymer (A1) having a hydrolyzable silyl group by hydrosilylation of a polyoxyalkylene polymer (B) having an allyl group with a hydrosilane compound (C); and reacting the polyoxyalkylene polymer (A1) with a hydroxyl group-containing compound (E) to produce a polyoxyalkylene polymer (A), wherein the polyoxyalkylene polymer (A) has a number average molecular weight of more than 3,000, the hydrosilylation is carried out in the presence of a hydrosilylation catalyst (D), and the polyoxyalkylene polymer (A1) is a compound 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 from 1 to 20 carbon atoms, and a is 0, 1, or 2. The polyoxyalkylene polymer (A1) has a Si—H group or contains a compound having a Si—H group.

2. The method for producing a polyoxyalkylene polymer according to claim 1, wherein the polyoxyalkylene polymer (A1) has a hydrolyzable silyl group (a2-1) containing a Si-H group.

3. The hydrolyzable silyl group (a2-1) is represented by the following formula (2): (2) (In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２ (a2-2) is a hydrolyzable silyl group represented by the following formula (1):

4. In the polyoxyalkylene polymer (A), the total number N of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2-2), 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 The ratio of N ａ１ / N ３ ｔ is 0.85 or more and 1.00 or less, ｔ The number N of the hydrolyzable silyl groups (a2-2) relative to ａ２－２ The ratio of N ａ２－２ / N ３ ｔ The method for producing a polyoxyalkylene polymer according to claim 3, wherein the m is 0.00 or more and less than 0.

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5. The above N ａ１ / N ３ ｔ The method for producing a polyoxyalkylene polymer according to claim 4, wherein the ratio is 0.95 or more and 1.00 or less.

6. The method for producing a polyoxyalkylene polymer according to any one of claims 1 to 5, wherein the hydrosilylation reaction catalyst (D) is a ruthenium complex (D1).

7. The method for producing a polyoxyalkylene polymer according to claim 6, wherein the ruthenium complex (D1) has a ligand (F1) derived from a compound (F), the compound (F) 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.

8. The method for producing a polyoxyalkylene polymer according to claim 7, wherein the compound (F) has a benzene ring skeleton or a norbornadiene skeleton.

9. The method for producing a polyoxyalkylene polymer according to claim 7, wherein the compound (F) 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.

10. The method for producing a polyoxyalkylene polymer according to claim 7, wherein the compound (F) 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.

11. The method for producing a polyoxyalkylene polymer according to claim 6, wherein the hydrosilylation is carried out in the presence of a compound (F), the compound (F) 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 a double bond to the carbon-carbon.

12. The method for producing a polyoxyalkylene polymer according to claim 11, wherein the compound (F) has a benzene ring skeleton or a norbornadiene skeleton.

13. The method for producing a polyoxyalkylene polymer according to claim 11, wherein the compound (F) 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.

14. The method for producing a polyoxyalkylene polymer according to claim 11, wherein the compound (F) 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.

15. The method for producing a polyoxyalkylene polymer according to any one of claims 1 to 5, wherein the hydrosilylation uses 3.0 moles or more of the hydrosilane compound (C) per 1.0 mole of the allyl group in the polyoxyalkylene polymer (B).

16. A polyoxyalkylene polymer having a hydrolyzable silyl group, 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.) and may have a Si—H group, and in the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of the Si—H groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is １ ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N １ ｔ is 0.85 or more and 1.00 or less, １ ｔ The number N of the Si-H groups Ｓｉ－Ｈ The ratio of N Ｓｉ－Ｈ / N １ ｔ A polyoxyalkylene polymer in which the value is 0.00 or more and less than 0.

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17. The polyoxyalkylene polymer may have a hydrolyzable silyl group (a2-1) containing a Si—H group, and in the polyoxyalkylene polymer, the total number N of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2-1), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is ２ ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ２ ｔ is 0.85 or more and 1.00 or less, ２ ｔ The number N of the hydrolyzable silyl groups (a2-1) relative to ａ２－１ The ratio of N ａ２－１ / N ２ ｔ The polyoxyalkylene polymer according to claim 16, wherein the polyoxyalkylene polymer is 0.00 or more and less than 0.

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18. The polyoxyalkylene polymer is represented by the following formula (2): (2) (In formula (2), R １ , R ２ , and a is R in formula (1). １ , R ２ and a are the same as a, b is 1 or 2, and a+b is 1 or more and 3 or less. In the polyoxyalkylene polymer, the total N of the number of the hydrolyzable silyl groups (a1), the number of the hydrolyzable silyl groups (a2-2), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups is ３ ｔ The number N of the hydrolyzable silyl groups (a1) relative to ａ１ The ratio of N ａ１ / N ３ ｔ is 0.85 or more and 1.00 or less, ３ ｔ N ａ２－２ / N ３ ｔ The polyoxyalkylene polymer according to claim 17, wherein the polyoxyalkylene polymer is 0.00 or more and less than 0.

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19. The above N ａ１ / N １ ｔ The polyoxyalkylene polymer according to claim 16, wherein the polyoxyalkylene polymer is 0.95 or more and 1.00 or less.

20. A curable composition comprising the polyoxyalkylene polymer according to any one of claims 16 to 19 and a curing catalyst.

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

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