Method for producing an oxyalkylene polymer having a carbon-carbon unsaturated group at the terminal, method for producing an oxyalkylene polymer having a reactive silicon group at the terminal, an oxyalkylene polymer having a carbon-carbon unsaturated group at the terminal, and an oxyalkylene polymer having a reactive silicon group at the terminal

Abstract

To provide: a production method of an oxyalkylene polymer having a carbon-carbon unsaturated group capable of introducing a reactive silicon group to its terminal at a high introduction rate while the oxyalkylene polymer can be obtained with a simplified process having a low environmental load; a production method of an oxyalkylene polymer having a reactive silicon group at its terminal, which is obtained from the oxyalkylene polymer having the carbon-carbon unsaturated group at the terminal; the oxyalkylene polymer having the carbon-carbon unsaturated group at the terminal; and the oxyalkylene polymer having the reactive silicon group at the terminal.SOLUTION: In a production method of an oxyalkylene polymer (X), a hydroxy group possessed by an oxyalkylene polymer (A) and an epoxy group possessed by an alicyclic epoxy compound (B) are made to react with each other in the presence of a composite metal cyanide complex catalyst. The oxyalkylene polymer (A) has the hydroxy group at least at one of its terminals, the alicyclic epoxy compound (B) has a substituent (a) having a carbon-carbon unsaturated group (however, an allyl group is to be excluded), and the oxyalkylene polymer (X) has the carbon-carbon unsaturated group originating from the substituent (a) at its terminal.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminal, a method for producing an oxyalkylene polymer having a reactive silicon group at its terminal, an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminal, and an oxyalkylene polymer having a reactive silicon group at its terminal.

Background Art

[0002] Conventionally, various methods have been proposed for introducing a reactive carbon-carbon unsaturated group into the terminal hydroxyl group of an oxyalkylene polymer, and further converting the carbon-carbon unsaturated group into a reactive silicon group to obtain an oxyalkylene polymer having a reactive silicon group at its terminal.

[0003] For example, Patent Document 1 describes a method in which the terminal hydroxyl group of an oxyalkylene polymer is converted into a metal alkoxide and then converted into an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminal using an allyl halide such as allyl chloride, and further converting the carbon-carbon unsaturated group into a reactive silicon group. Further, Patent Document 2 describes a method in which the terminal hydroxyl group of an oxyalkylene polymer is converted into a metal alkoxide and then converted into an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminal using a methylpropene halide such as 3-chloro-2-methyl-1-propene, and further converting the carbon-carbon unsaturated group into a reactive silicon group. Further, Patent Document 3 describes a method in which an alkali metal salt is allowed to act on an oxyalkylene polymer having a hydroxyl group at its terminal, then an epoxy compound having a carbon-carbon unsaturated bond is reacted, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted to convert it into an oxyalkylene polymer having a carbon-carbon unsaturated group, and further converting the carbon-carbon unsaturated group into a reactive silicon group.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-88148 [Patent Document 2] Japanese Patent Publication No. 2000-345023 [Patent Document 3] International Publication No. 2013 / 180203 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in the methods described in references 1 and 2, when reacting an oxyalkylene polymer with a metal alkoxide introduced at its terminus with an allyl halide or methylpropene halide, a crystallization step is required to remove the by-product metal halide in order to expedite the subsequent conversion to reactive silicon groups. This crystallization step generates a large amount of wastewater, resulting in a high environmental burden and a complicated manufacturing process. Furthermore, in the methods described in References 1 and 3, when the allyl groups at the ends of the oxyalkylene polymer having carbon-carbon unsaturated groups are converted to reactive silicon groups, a certain percentage of double bond rearrangements occur, which leads to a problem in that the rate of introduction of reactive silicon groups decreases.

[0006] The present invention aims to solve these problems and to provide a method for producing an oxyalkylene polymer having a terminal carbon-carbon unsaturated group that can introduce reactive silicon groups at a high rate, using a simplified process with low environmental impact; a method for producing an oxyalkylene polymer having a terminal reactive silicon group obtained from the oxyalkylene polymer having a terminal carbon-carbon unsaturated group; the oxyalkylene polymer having a terminal carbon-carbon unsaturated group; and the oxyalkylene polymer having a terminal reactive silicon group. [Means for solving the problem]

[0007] The present invention is based on the discovery that an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminus, obtained using a predetermined alicyclic epoxy compound (B), can be produced without undergoing a crystallization process, and that reactive silicon groups can be introduced with a high rate.

[0008] The present invention provides the following means. [1] A method for producing an oxyalkylene polymer (X) in which a hydroxyl group of an oxyalkylene polymer (A) is reacted with an epoxy group of an alicyclic epoxy compound (B) in the presence of a complex metal cyanide catalyst, The oxyalkylene polymer (A) has at least one hydroxyl group at its terminus, The alicyclic epoxy compound (B) has substituents (a) having carbon-carbon unsaturated groups (excluding allyl groups), A method for producing the oxyalkylene polymer (X), wherein the oxyalkylene polymer (X) has a carbon-carbon unsaturated group derived from the substituent (a) at its terminal. [2] A method for producing the oxyalkylene polymer (X) according to [1], wherein the number average molecular weight of the oxyalkylene polymer (A) is 2,000 to 50,000. [3] A method for producing the oxyalkylene polymer (X) according to [1] or [2] above, wherein the average number of hydroxyl groups per molecule of the oxyalkylene polymer (A) is 1 to 8. [4] A method for producing the oxyalkylene polymer (X) according to any one of [1] to [3] above, wherein the oxyalkylene polymer (A) includes constituent units derived from propylene oxide. [5] The oxyalkylene polymer (A) further comprises constituent units derived from ethylene oxide, A method for producing the oxyalkylene polymer (X) according to [4], wherein the ratio of the constituent units derived from ethylene oxide to all constituent units of the oxyalkylene polymer (A) is 1 to 30% by mass. [6] A method for producing an oxyalkylene polymer (X) according to any one of [1] to [5] above, wherein the alicyclic skeleton of the alicyclic epoxy compound (B) is a monocyclic or polycyclic structure with 3 to 12 ring-forming carbon atoms. [7] A method for producing the oxyalkylene polymer (X) according to any one of [1] to [6] above, wherein the alicyclic epoxy compound (B) is a compound represented by the following formula (i). [ka] (In formula (i), R 1 ~R 4 One selected from represents the substituent (a), R other than substituent(a) 1 ~R 4 (This represents a hydrogen atom.) [8] The aforementioned R 2 or R 3 A method for producing the oxyalkylene polymer (X) described in [7] above, wherein the substituent (a) is the substituent (a). [9] A method for producing an oxyalkylene polymer (X) according to any one of [1] to [8] above, wherein the substituent (a) is at least one selected from the group consisting of a vinyl group, a vinyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a propargyl group.

[10] A method for producing an oxyalkylene polymer (X) according to any one of [1] to [9] above, wherein the alicyclic epoxy compound (B) is at least one selected from the group consisting of 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[11] A method for producing an oxyalkylene polymer (Y) by reacting the carbon-carbon unsaturated group having at the terminal end of an oxyalkylene polymer (X) obtained by any of the production methods described in [1] to

[10] above with a hydrosilane compound (C) having a hydrolyzable group represented by the following formula (ii), The method for producing the oxyalkylene polymer (Y) having a reactive silicon group at the terminal. -SiX n R 3-n (ii) (In formula (ii), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group having 1 to 20 carbon atoms, n is an integer from 1 to 3, When n is 1, the plurality of Rs may be the same or different, When n is 2 or 3, the plurality of Xs may be the same or different. However, R excludes hydrolyzable groups.)

[12] An oxyalkylene polymer (X1) having a carbon-carbon unsaturated group at the terminal and having a group represented by the following formula (1) at the terminal.

Chemical formula

[13] An oxyalkylene polymer (Y1) having a reactive silicon group at the terminal and having a group represented by the following formula (2) at the terminal.

Chemical formula

[14] The hydroxyl group of the group represented by the following formula (1) at the terminal of the oxyalkylene polymer (X) obtained by the manufacturing method described in [7] or [8] above is converted to a metal alkoxide with an alkali metal alkoxide, and then reacted with an organic halogen compound having an unsaturated bond at the terminal to obtain an oxyalkylene polymer (X2) with a substituent (b) having a carbon-carbon unsaturated group. A method for producing an oxyalkylene polymer (Y2) having two reactive silicon groups at its termini, comprising reacting the carbon-carbon unsaturated group of substituent (a) and the carbon-carbon unsaturated group of substituent (b) in the oxyalkylene polymer (X2) with a hydrolyzable group represented by the following formula (ii), wherein The oxyalkylene polymer (Y2) has two reactive silicon groups at its terminal ends, and the method for producing the oxyalkylene polymer (Y2). [ka] (In formula (1), R 1 ~R 4 One selected from represents the substituent (a), R other than substituent(a) 1 ~R 4This represents a hydrogen atom, *a represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (X). -SiX n R 3-n (ii) (In formula (ii), X represents a hydrolyzable group or a hydroxyl group. R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer from 1 to 3. When n is 1, multiple Rs can be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different. However, R excludes hydrolyzable groups.

[15] An oxyalkylene polymer (Y2) having two reactive silicon groups at its terminus, with a group represented by the following formula (3) at its terminus. [ka] (In formula (3), R 5 ~R 8 One of the selected elements is the base represented by the following formula (iii): R is not a group represented by formula (iii) above. 5 ~R 8 This represents a hydrogen atom, R 10 This represents a divalent organic group derived from substituent (b) having a carbon-carbon unsaturated group. X represents a hydrolyzable group or a hydroxyl group. R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer from 1 to 3. When n is 1, multiple Rs can be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different. However, R excludes hydrolyzable groups. *c represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (Y2). -R 9 -SiX n R3-n (iii) (In formula (iii), R 9 This represents a divalent organic group derived from substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), X, R, and n are defined as in equation (3). [Effects of the Invention]

[0009] According to the present invention, an oxyalkylene polymer having a carbon-carbon unsaturated group at its terminus, which can introduce reactive silicon groups at a high rate, can be obtained through a simplified process with a low environmental impact. Furthermore, a method for producing an oxyalkylene polymer having a reactive silicon group at its terminus, obtained from the aforementioned oxyalkylene polymer having a carbon-carbon unsaturated group at its terminus, and an oxyalkylene polymer having a reactive silicon group at its terminus are provided. In addition, a method for producing an oxyalkylene polymer having two reactive silicon groups at its terminus, and an oxyalkylene polymer having two reactive silicon groups at its terminus are provided.

[0010] The definitions and meanings of terms and notations used in this specification are given below. The "hydroxyl value" is determined by measurement in accordance with JIS K1557-1:2007. The "molecular weight on a hydroxyl value basis" is calculated using the formula: 56100 / (hydroxyl value) × (number of active hydrogen atoms in the initiator). "Carbon-carbon unsaturated group content" refers to the amount of carbon-carbon unsaturated groups [mmol / g] in the product obtained by introducing carbon-carbon unsaturated groups to the terminal hydroxyl groups of an oxyalkylene polymer. 1 It is determined by the internal standard method of 1H-NMR. Specifically, it is determined by the method described in the examples below.

[0011] "Reactive silicon group content" refers to the amount of reactive silicon groups [mmol / g] in the product obtained by reacting a carbon-carbon unsaturated group at the terminal end of an oxyalkylene polymer (X), an oxyalkylene polymer (X1), or an oxyalkylene polymer (X2) with a hydrolyzable hydrosilane compound (C), and then removing the unreacted hydrosilane compound (C) by defoliation. 1 It is determined by the internal standard method of 1H-NMR. Specifically, it is determined by the method described in the examples below. The "reactive silicon group introduction rate" is the percentage of carbon-carbon unsaturated groups at the terminals of the oxyalkylene polymer (X) that have been converted into reactive silicon groups. 1 It is calculated using values ​​obtained from the internal standard method of H-NMR. Specifically, it is obtained by the method described in the examples below. "Propenyl group content" refers to the amount of propenyl groups [mmol / g] in the product obtained by reacting a carbon-carbon unsaturated group at the terminal end of an oxyalkylene polymer (X), an oxyalkylene polymer (X1), or an oxyalkylene polymer (X2) with a hydrolyzable hydrosilane compound (C), and then removing the unreacted hydrosilane compound (C) by defoliation. 1 It is determined by 1H-NMR. Specifically, it is determined by the method described in the examples below. "Propenyl group percentage" refers to the percentage of propenyl groups remaining in the product obtained by reacting an oxyalkylene polymer (X), an oxyalkylene polymer (X1), or an oxyalkylene polymer (X2) with a hydrolyzable hydrosilane compound (C), after removing the unreacted hydrosilane compound (C) by defoliation (the ratio of the number of propenyl groups to the total number of terminal carbon-carbon unsaturated groups) [mol%]. 1 It is determined by the internal standard method of 1H-NMR. Specifically, it is determined by the method described in the examples below.

[0012] [Method for producing oxyalkylene polymer (X)] The present invention provides a method for producing an oxyalkylene polymer (X) by reacting a hydroxyl group of an oxyalkylene polymer (A) with an epoxy group of an alicyclic epoxy compound (B) in the presence of a complex metal cyanide catalyst, wherein the oxyalkylene polymer (A) has the hydroxyl group at at least one terminal, the alicyclic epoxy compound (B) has a substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), and the oxyalkylene polymer (X) has a carbon-carbon unsaturated group at its terminal derived from substituent (a).

[0013] By using an alicyclic epoxy compound (B) having an alicyclic skeleton and a substituent (a) having a carbon-carbon unsaturated group other than an allyl group, it is possible to produce an oxyalkylene polymer (X) having a carbon-carbon unsaturated group at the terminal without going through a crystallization step, because no by-product salts are formed. In other words, an oxyalkylene polymer (X) having a carbon-carbon unsaturated group can be produced in a simplified process with a low environmental impact. Furthermore, when an oxyalkylene polymer (X) is produced using the alicyclic epoxy compound (B) of the present invention, the carbon-carbon unsaturated groups at the terminals do not undergo double bond rearrangement when converted to reactive silicon groups. Therefore, compared to conventional oxyalkylene polymers having allyl-type carbon-carbon unsaturated groups at the terminals, a higher rate of reactive silicon group introduction is possible.

[0014] The amount of alicyclic epoxy compound (B) used when reacting the hydroxyl groups of the oxyalkylene polymer (A) with the epoxy groups of the alicyclic epoxy compound (B) can be appropriately set according to the reactivity, the amount of carbon-carbon unsaturated groups introduced at the terminals (amount of unsaturated groups), manufacturing costs, etc., but is preferably 0.50 to 1.50 moles, more preferably 0.80 to 1.40 moles, and even more preferably 0.95 to 1.30 moles per mole of hydroxyl groups of the oxyalkylene polymer (A).

[0015] When reacting the hydroxyl groups of the oxyalkylene polymer (A) with the epoxy groups of the alicyclic epoxy compound (B), it is preferable to sequentially add the alicyclic epoxy compound (B) to the oxyalkylene polymer (A) under a nitrogen or inert gas atmosphere. The temperature of the oxyalkylene polymer (A) when sequentially adding the alicyclic epoxy compound (B) is set appropriately according to the reactivity, but is preferably in the range of 100 to 200°C, more preferably in the range of 110 to 180°C, and even more preferably in the range of 120 to 160°C.

[0016] The time for sequentially adding the alicyclic epoxy compound (B) is set appropriately depending on the reactivity, but is preferably 1 to 20 hours, more preferably 2 to 15 hours, and even more preferably 3 to 12 hours.

[0017] After sequentially adding the alicyclic epoxy compound (B), it is preferable to further heat the solution containing the sequentially added alicyclic epoxy compound (B) under a nitrogen or inert gas atmosphere, from the viewpoint of allowing sufficient reaction between the hydroxyl groups of the oxyalkylene polymer (A) and the epoxy groups of the alicyclic epoxy compound (B). The temperature is preferably the same as the temperature of the oxyalkylene polymer (A) when the alicyclic epoxy compound (B) is sequentially added. The heating time is preferably 0.5 to 20 hours, more preferably 0.7 to 15 hours, and even more preferably 0.8 to 10 hours.

[0018] Examples of terminal carbon-carbon unsaturated groups include vinyl groups (-CH=CH2) and ethynyl groups (-C≡CH). Of these, vinyl groups are preferred from the viewpoint of introducing reactive silicon groups at a high rate. Oxyalkylene polymers (X) having carbon-carbon unsaturated groups at their terminals are useful as precursors for oxyalkylene polymers having reactive silicon groups at their terminals.

[0019] (Oxyalkylene polymer (A)) The oxyalkylene polymer (A) is a raw material for the oxyalkylene polymer (X) having a carbon-carbon unsaturated group at one of its terminals, and has the aforementioned hydroxyl group at at least one terminal. The oxyalkylene polymer (A) preferably does not have an allyl group. As the oxyalkylene polymer (A), a compound obtained by ring-opening polymerization of alkylene oxide in the presence of a catalyst with an initiator having an active hydrogen group is preferred.

[0020] The average number of hydroxyl groups per molecule of the oxyalkylene polymer (A) usually corresponds to the number of active hydrogens in the initiator, and is preferably 1 to 8, more preferably 1 to 7, and even more preferably 1 to 6. Within the above range for the average number of hydroxyl groups, the manufacturing method of the present invention makes it easy to efficiently convert to carbon-carbon unsaturated groups.

[0021] From the viewpoint of efficiently converting the hydroxyl groups of the oxyalkylene polymer (A) into carbon-carbon unsaturated groups, the number-average molecular weight of the oxyalkylene polymer (A) in terms of polystyrene, as determined by gel permeation chromatography, is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and even more preferably 2,000 to 50,000.

[0022] From the viewpoint of efficiently converting the hydroxyl groups of the oxyalkylene polymer (A) into carbon-carbon unsaturated groups, the molecular weight of the oxyalkylene polymer (A) in terms of hydroxyl value is preferably 1500 to 12000, more preferably 2000 to 90000, even more preferably 3000 to 75000, and even more preferably 4500 to 50000.

[0023] Examples of the active hydrogen-containing group of the initiator include hydroxyl groups, carboxyl groups, and amino groups, with hydroxyl groups being preferred and alcoholic hydroxyl groups being more preferred. Examples of initiators include alcohols, phenols, carboxylic acids, and amines, with aliphatic alcohols being preferred. Alternatively, an oxyalkylene polymer having hydroxyl groups with a lower molecular weight than the oxyalkylene polymer (A) may also be used as an initiator. One of these initiators may be used alone, or two or more may be used in combination. The number of carbon atoms in the aliphatic alcohol initiator is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6.

[0024] Examples of aliphatic alcohols used as initiators include methanol, ethanol, 2-propanol, n-butanol, isobutanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, allyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, diglycerin, and dipentaerythritol. Of these, n-butanol, propylene glycol, and sorbitol are preferred from the viewpoint of availability and other factors.

[0025] The alkylene oxide preferably has 2 to 4 carbon atoms. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, and may be used alone or in combination of two or more. Of these, ethylene oxide and propylene oxide are preferred from the viewpoint of availability, and propylene oxide is more preferred. In other words, it is more preferable that the oxyalkylene polymer (A) contains constituent units derived from propylene oxide. Furthermore, it is preferable to use both ethylene oxide and propylene oxide as alkylene oxides. That is, the oxyalkylene polymer (A) may contain constituent units derived from propylene oxide, and may also contain constituent units derived from ethylene oxide. In this case, from the viewpoint of water resistance, it is more preferable that the proportion of constituent units derived from ethylene oxide to all constituent units of the oxyalkylene polymer (A) is 1 to 30% by mass.

[0026] Known catalysts can be used for ring-opening polymerization of alkylene oxides. Examples include alkaline catalysts such as potassium hydroxide, transition metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrin, complex metal cyanide catalysts, and catalysts consisting of phosphazene compounds. Of these, complex metal cyanide complex catalysts are preferred from the viewpoint of homogenizing the molecular weight distribution, and examples include zinc hexacyanocobaltate complexes with tert-butanol as a ligand. A known method can be applied to the production method of the oxyalkylene polymer (A) using a complex metal cyanide catalyst. For example, the production methods disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Publication No. 2004-269776, Japanese Patent Publication No. 2005-15786, International Publication No. 2013 / 065802, Japanese Patent Publication No. 2015-010162, etc., can be adopted.

[0027] (Alicyclic epoxy compound (B)) The alicyclic epoxy compound (B) has a substituent (a) having a carbon-carbon unsaturated group. However, the substituent (a) having a carbon-carbon unsaturated group at the terminal end does not include an allyl group. Furthermore, in the present invention, the alicyclic epoxy compound (B) has an epoxy group composed of two adjacent carbon atoms and one oxygen atom that constitute an alicyclic skeleton.

[0028] Examples of carbon-carbon unsaturated groups that substituent (a) may have include vinyl groups (-CH=CH2) and ethynyl groups (-C≡CH). Of these, vinyl groups are preferred from the viewpoint of introducing reactive silicon groups at a high rate. From the viewpoint of introducing reactive silicon groups with a high rate, the substituent (a) of the alicyclic epoxy compound (B) is preferably a vinyl group, a vinyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a propargyl group, and more preferably a vinyl group and a (meth)acryloyloxy group.

[0029] The alicyclic epoxy compound (B) may have substituents other than substituent (a), but it is preferable that it does not have an allyl group as a substituent, and more preferably that it does not have any substituents at all.

[0030] From the viewpoint of introducing reactive silicon groups at a high rate, the alicyclic skeleton of the alicyclic epoxy compound (B) is preferably a monocyclic or polycyclic structure with 3 to 12 ring-forming carbon atoms. From the viewpoint of availability and other factors, the number of ring-forming carbon atoms in the alicyclic skeleton is preferably 4 to 10, more preferably 5 to 8, and even more preferably 6. From the viewpoint of availability and other factors, the alicyclic skeleton is preferably a monocyclic structure. The alicyclic skeleton may be saturated or unsaturated, but it is preferably a saturated ring.

[0031] Examples of alicyclic skeletons include cycloalkane rings, cycloalkene rings, bicycloalkane rings, bicycloalkene rings, and tricycloalkane rings. Among these, cycloalkane rings are preferred, more preferably cycloalkane rings having 5 to 8 carbon atoms, and even more preferably cyclohexane rings.

[0032] From the viewpoint of introducing reactive silicon groups with a high rate, the alicyclic epoxy compound (B) is preferably a compound represented by the following formula (i).

[0033] [ka]

[0034] In formula (i), R 1 ~R 4 One of the selected R represents substituent (a) and R does not represent substituent (a). 1 ~R 4 This represents a hydrogen atom. From the perspective of introducing reactive silicon groups with a high introduction rate, R 2 or R 3 However, it is preferable that the substituent (a) is as described above.

[0035] Examples of the "carbon-carbon unsaturated group" of substituent (a) include a vinyl group (-CH=CH2) and an ethynyl group (-C≡CH). Of these, the vinyl group is preferred from the viewpoint of introducing reactive silicon groups at a high rate. From the viewpoint of introducing reactive silicon groups with a high introduction rate, the substituent (a) is preferably a vinyl group, a vinyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a propargyl group, and more preferably a vinyl group and a (meth)acryloyloxy group.

[0036] From the viewpoint of introducing reactive silicon groups at a high rate, the alicyclic epoxy compound (B) is preferably at least one selected from the group consisting of 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate, and more preferably 1-vinyl-3,4-epoxycyclohexane.

[0037] (Composite metal cyanide complex catalyst) Examples of composite metal cyanide complex catalysts include those similar to those used in the ring-opening polymerization of alkylene oxides. From the viewpoint of efficiently converting to carbon-carbon unsaturated groups, a zinc hexacyanocobaltate complex with tert-butanol as a ligand is preferred as the composite metal cyanide complex catalyst.

[0038] [Method for producing an oxyalkylene polymer (Y) having reactive silicon groups at its termini] The present invention provides a method for producing an oxyalkylene polymer (Y) having a reactive silicon group at its terminus, wherein the carbon-carbon unsaturated group at the terminus of the oxyalkylene polymer (X) obtained by the above-described "Method for producing an oxyalkylene polymer (X) having a carbon-carbon unsaturated group at its terminus" is reacted with a hydrolyzable group (C) represented by the following formula (ii), and the oxyalkylene polymer (Y) has a reactive silicon group at its terminus. -SiX n R 3-n (ii) In formula (ii), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group having 1 to 20 carbon atoms, and n is an integer from 1 to 3. When n is 1, multiple Rs may be the same or different, and when n is 2 or 3, multiple Xs may be the same or different. However, R is not a hydrolyzable group.

[0039] By adding a hydrosilane compound (C) to the carbon-carbon unsaturated group at the terminal of the oxyalkylene polymer (X) via a hydrosilylation reaction, an oxyalkylene polymer (Y) having a reactive silicon group at its terminal is obtained.

[0040] Preferred hydrolyzable groups of X include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, and aminooxy groups. Examples include alkoxy groups with 1 to 4 carbon atoms such as methoxy and ethoxy groups; acyloxy groups such as acetoxy groups; ketoximate groups such as acetoximate and dimethylketoximate groups; amino groups such as N,N-dimethylamino groups; and amide groups such as N-methylacetamide groups. Of these, methoxy and ethoxy groups are more preferred.

[0041] The monovalent organic group represented by R is preferably a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group. The hydrocarbon group R is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The halogenated hydrocarbon group R is preferably an alkyl group having one or more chlorine or fluorine atoms, and the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0042] n is an integer between 1 and 3, preferably 1 or 2, and more preferably 2.

[0043] Specific examples of hydrosilane compounds (C) include halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, methoxymethyldichlorosilane, dimethoxymethyldichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, and (3,3,3-trifluoropropyl)dimethyl Toxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl Examples include alkoxysilanes such as [dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone-free type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane. Of these, dimethoxymethylsilane is preferred from the viewpoint of high activity and good curability in curable compositions.

[0044] The amount of hydrosilane compound (C) used is set appropriately depending on the reactivity, etc., but is preferably 0.05 to 10 moles, more preferably 0.1 to 5 moles, even more preferably 0.5 to 3 moles, and even more preferably 1.0 to 2.0 moles per mole of carbon-carbon unsaturated groups of the oxyalkylene polymer (X) having carbon-carbon unsaturated groups at its terminals.

[0045] The reaction between an oxyalkylene polymer (X) having a carbon-carbon unsaturated group at its terminus and a hydrosilane compound (C) is preferably carried out in the presence of a catalyst to promote the hydrosilylation reaction. Examples of catalysts include metals such as platinum, palladium, rhodium, ruthenium, iridium, iron, and cobalt, as well as complexes thereof. Of these, chloroplatinic acid, platinum-olefin complexes, and platinum-vinylsiloxane complexes are preferred from the viewpoint of reaction efficiency, with chloroplatinic acid and platinum-vinylsiloxane complexes being more preferred.

[0046] The reaction between an oxyalkylene polymer (X) having a carbon-carbon unsaturated group at its terminus and a hydrosilane compound (C) is preferably carried out under heating from the viewpoint of lowering the viscosity of the reaction system and promoting the reaction. The reaction temperature is preferably 50 to 150°C, more preferably 60 to 130°C, and even more preferably 70 to 120°C. The reaction time is preferably 0.5 to 15 hours, more preferably 1 to 12 hours, and even more preferably 2 to 10 hours from the viewpoint of allowing the hydrosilylation reaction to proceed sufficiently.

[0047] [Method for producing an oxyalkylene polymer (Y2) having two reactive silicon groups at its terminus] The present invention provides a method for producing an oxyalkylene polymer (Y2) having two reactive silicon groups at its termini, wherein the compound represented by formula (i) above is used as the alicyclic epoxy compound (B), the hydroxyl group of the group represented by formula (1) below at the termini of the oxyalkylene polymer (X) obtained by the above production method is converted to a metal alkoxide with an alkali metal alkoxide, and then reacted with an organic halogen compound having an unsaturated bond at the termini to obtain an oxyalkylene polymer (X2) having a substituent (b) having a carbon-carbon unsaturated group, and the carbon-carbon unsaturated group of substituent (a) and the carbon-carbon unsaturated group of substituent (b) in the oxyalkylene polymer (X2) is reacted with a hydrolyzable group represented by formula (ii) below, wherein the oxyalkylene polymer (Y2) has two reactive silicon groups at its termini.

[0048] [ka]

[0049] In formula (1), R 1 ~R 4 One of the selected R represents substituent (a) and R does not represent substituent (a). 1 ~R 4 * represents a hydrogen atom, and *a represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (X).

[0050] -SiX n R 3-n (ii) In formula (ii), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group having 1 to 20 carbon atoms, and n is an integer from 1 to 3. When n is 1, multiple Rs may be the same or different, and when n is 2 or 3, multiple Xs may be the same or different. However, R is not a hydrolyzable group.

[0051] Examples of alkali metal alkoxides include sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, and potassium tert-butoxide. Of these, sodium methoxide and sodium ethoxide are preferred from the viewpoint of availability and other factors.

[0052] From the viewpoint of sufficiently and efficiently promoting the conversion to metal alkoxides, the amount of alkali metal alkoxide used is preferably such that there are 1.0 to 5.0 moles of alkoxy groups per mole of hydroxyl groups at the terminals of the oxyalkylene polymer (X), more preferably 1.05 to 4.0 moles, even more preferably 1.1 to 3.0 moles, and even more preferably 1.15 to 2.0 moles.

[0053] The conversion of alkali metal alkoxides to metal alkoxides is preferably carried out under a nitrogen or inert gas atmosphere, and the reaction temperature and reaction time are preferably in the range of, for example, 100 to 150°C and 0.5 to 24 hours.

[0054] In the reaction between the metal alkoxide and the organic halogen compound having an unsaturated bond at its terminus, an ether bond is formed between the residue obtained by removing the alkali metal from the metal alkoxide and the residue obtained by removing the halogen atom from the organic halogen compound, yielding an oxyalkylene polymer (X2). The group formed by the ether bond between the residue obtained by removing the alkali metal from the metal alkoxide and the residue obtained by removing the halogen atom from the organic halogen compound is substituent (b). The details of the "carbon-carbon unsaturated group" of substituent (b) are the same as those of the "carbon-carbon unsaturated group" of substituent (a), and the preferred embodiment is also the same. Examples of substituents (b) include vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-methylallyloxy group, 1-pentenyloxy group, 2-methyl-2-butenyloxy group, 1-hexenyloxy group, and 2-methyl-2-pentenyloxy group. Of these, the allyloxy group is preferred from the viewpoint of ease of production.

[0055] Examples of organic halogen compounds having an unsaturated bond at the terminal include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, methallyl iodide, 1-bromo-2-butine, 4-bromo-1-butine, 1-bromo-2-octyne, 1-bromo-2-pentine, 1,4-dibromo-2-butine, 5-bromo-1-pentine, 6-bromo-1-hexine, vinyl iodide, and allyl iodide. Of these, allyl chloride, methallyl chloride, and propargyl bromide are preferred from the viewpoint of ease of handling, and allyl chloride and methallyl chloride are more preferred.

[0056] The amount of organic halogen compound having an unsaturated bond at the terminal is preferably such that there is an excess amount of the organic halogen compound per mole of hydroxyl groups at the terminal of the oxyalkylene polymer (X) having an unsaturated bond at the terminal, for example, 1.0 to 10.0 moles, from the viewpoint of sufficiently and efficiently promoting the conversion to substituent (b) having a carbon-carbon unsaturated group.

[0057] The reaction temperature and reaction time when converting to substituent (b) having a carbon-carbon unsaturated group are preferably in the range of, for example, 100 to 150°C and 0.5 to 24 hours.

[0058] By converting to substituent (b) having a carbon-carbon unsaturated group, an oxyalkylene polymer (X2) is obtained that has substituent (a) having a carbon-carbon unsaturated group and substituent (b) having a carbon-carbon unsaturated group, i.e., has two carbon-carbon unsaturated groups.

[0059] Preferred embodiments of X, R, and n in formula (ii) are the same as those described in the [method for producing an oxyalkylene polymer (Y) having reactive silicon groups at its termini] above.

[0060] Specific examples of the hydrosilane compound (C) are as described in the above [Method for producing an oxyalkylene polymer (Y) having a reactive silicon group at its terminus].

[0061] The amount of hydrosilane compound (C) used is set appropriately depending on the reactivity, etc., but is preferably 0.05 to 10 moles, more preferably 0.1 to 5 moles, even more preferably 0.5 to 3 moles, and even more preferably 1.0 to 2.0 moles, per 1 mole of the total carbon-carbon unsaturated groups of substituent (a) and substituent (b).

[0062] The reaction between the carbon-carbon unsaturated group of substituent (a) and the carbon-carbon unsaturated group of substituent (b) and the hydrosilane compound (C) is preferably carried out in the presence of a catalyst to promote the hydrosilylation reaction. Examples of catalysts include those described in [Method for Producing Oxyalkylene Polymer (Y)], and preferred embodiments are also similar.

[0063] A preferred embodiment of the reaction between the carbon-carbon unsaturated group of substituent (a) and the carbon-carbon unsaturated group of substituent (b) and the hydrosilane compound (C) is the same as in the [method for producing an oxyalkylene polymer (Y) having reactive silicon groups at its termini].

[0064] [Oxyalkylene polymer having carbon-carbon unsaturated groups at its terminals (X1)] The oxyalkylene polymer (X1) having a carbon-carbon unsaturated group at its terminus has a group represented by the following formula (1) at its terminus, and has a carbon-carbon unsaturated group at its terminus. It is obtained by the manufacturing method described above.

[0065] [ka]

[0066] In formula (1), R 1 ~R 4 One of the selected elements represents substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), and R is not substituent (a) having a carbon-carbon unsaturated group. 1 ~R 4 * represents a hydrogen atom, and *a represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (X1) having a carbon-carbon unsaturated group at its terminal end. From the viewpoint of introducing reactive silicon groups with a high rate into an oxyalkylene polymer (X1) having carbon-carbon unsaturated groups at its terminals, R 2 or R 3 However, it is preferable that the substituent (a) has the carbon-carbon unsaturated group.

[0067] R in equation (1) 1 ~R 4 A preferred embodiment of the substituent (a) represented by one selected from is the R described above in (alicyclic epoxy compound (B)). 1 ~R 4 This is similar to substituent (a) represented by one selected from the group.

[0068] Typical examples of the oxyalkylene polymer (X1) having a carbon-carbon unsaturated group at its terminus in the present invention include, for example, the compound represented by the following formula (X1-a).

[0069] [ka]

[0070] In equation (X1-a), k can be set appropriately according to the desired number-average molecular weight.

[0071] The oxyalkylene polymers (X) and (X1) having a carbon-carbon unsaturated group at the terminal end of the present invention are preferably compounds represented by the above formula (X1-a) from the viewpoint of introducing reactive silicon groups at a high rate.

[0072] [Oxyalkylene polymer having reactive silicon groups at the terminal (Y1)] The oxyalkylene polymer (Y1) having a reactive silicon group at its terminus has a group represented by the following formula (2) at its terminus, and has a reactive silicon group at its terminus. It is obtained by the manufacturing method described above.

[0073] [ka]

[0074] In formula (2), R 5 ~R 8 One of the selected groups is the group represented by the following formula (iii), and not the group represented by the aforementioned formula (iii). 5 ~R 8 * represents a hydrogen atom, and *b represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (Y1) having a reactive silicon group at its terminus. -R 9 -SiX n R 3-n (iii) In formula (iii), R 9 X represents a divalent organic group derived from a substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group having 1 to 20 carbon atoms, and n is an integer from 1 to 3. When n is 1, multiple Rs may be the same or different, and when n is 2 or 3, multiple Xs may be the same or different.

[0075] R 9 represents a divalent organic group derived from substituent (a), preferably a divalent organic group derived from at least one selected from the group consisting of vinyl group, vinyloxy group, (meth)acryloyl group, (meth)acryloyloxy group, and propargyl group, and more preferably a divalent organic group derived from vinyl group or (meth)acryloyloxy group.

[0076] The preferred embodiments of X, R, and n in formula (iii) are the same as the preferred embodiments of X, R, and n described above in the [Method for Producing an Oxyalkylene Polymer (Y) Having Reactive Silicon Groups at its Terminals].

[0077] Typical examples of the reactive silicon group-containing oxyalkylene polymer (Y1) of the present invention include, for example, the compound represented by the following formula (Y1-a).

[0078] [ka]

[0079] In equation (Y1-a), k can be set appropriately according to the desired number-average molecular weight.

[0080] The oxyalkylene polymers (Y) and (Y1) having a reactive silicon group in the present invention are preferably compounds represented by the above formula (Y1-a).

[0081] [Oxyalkylene polymer (Y2) having two reactive silicon groups at its terminus] The oxyalkylene polymer (Y2) having two reactive silicon groups at its termini has a group represented by the following formula (3) at its termini, and has two reactive silicon groups at its termini. It is obtained by the manufacturing method described above. [ka]

[0082] In formula (3), R 5 ~R 8 One of the selected groups is the group represented by the following formula (iii), and not the group represented by the aforementioned formula (iii). 5 ~R 8 represents a hydrogen atom, and R 10X represents a divalent organic group derived from substituent (b) having a carbon-carbon unsaturated group, X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group having 1 to 20 carbon atoms, and n is an integer from 1 to 3. When n is 1, multiple Rs may be the same or different, and when n is 2 or 3, multiple Xs may be the same or different. However, R excludes hydrolyzable groups. *c represents the bond position to the oxyalkylene chain in the oxyalkylene polymer having two reactive silicon groups at its terminus. -R 9 -SiX n R 3-n (iii) In formula (iii), R 9 represents a divalent organic group derived from substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), where X, R, and n are as defined in formula (3).

[0083] Details of the substituent (b) having a carbon-carbon unsaturated group are as described above in [Method for producing an oxyalkylene polymer (Y2) having two reactive silicon groups at its terminus], and the preferred embodiment is the same.

[0084] R 10 The divalent organic group derived from substituent (b) represented by is preferably a divalent organic group derived from an allyloxy group.

[0085] Preferred embodiments of X, R, and n in formulas (3) and (iii) are the same as those described in the [Method for Producing Oxyalkylene Polymer (Y)] above. R in equation (iii) 9 A preferred embodiment is the same as that of the above-described [oxyalkylene polymer having reactive silicon groups at its termini (Y1)].

[0086] A typical example of the oxyalkylene polymer (Y2) having two reactive silicon groups of the present invention is, for example, the compound represented by the following formula (Y2-a).

[0087] [ka]

[0088] In equation (Y2-a), l can be set appropriately according to the desired number-average molecular weight.

[0089] The oxyalkylene polymer (Y2) having two reactive silicon groups in the present invention is preferably a compound represented by the above formula (Y2-a). [Examples]

[0090] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0091] [Measurement method] The methods for measuring various physical properties in each example are as follows: [Hydrogen-based molecular weight of oxyalkylene polymer (A)] The hydroxyl value-based molecular weight (M) of the oxyalkylene polymer (A) was calculated using the following formula (a). M = 56100 / (Hydroxyl value of oxyalkylene polymer (A)) × (Number of active hydrogens in the initiator) (a) In formula (a), the hydroxyl value is the value calculated in accordance with Method B (potentiometric automatic titration) of JIS K1557-1:2007.

[0092] [Number average molecular weight of oxyalkylene polymer (A)] The number-average molecular weight of the oxyalkylene polymer (A) was measured by the same method as described in paragraph

[0086] of Japanese Patent Application Publication No. 2012-111813.

[0093] [Moisture content of oxyalkylene polymer (A)] The water content of oxyalkylene polymer (A) was measured in accordance with Method B of JIS K1557-2:2007.

[0094] [Carbon-carbon unsaturated group] A solution sample prepared by stirring and mixing approximately 900 mg of the product obtained in Examples 1-6 below (products containing oxyalkylene polymers (X1-1)-(X1-4), (X2-1), and (X2-2)), approximately 25 mg of p-dinitrobenzene, and approximately 6 g of deuterated chloroform. 1 1H-NMR was measured, and the amount of carbon-carbon unsaturated groups was calculated using the internal standard method with p-dinitrobenzene.

[0095] [Reactive silicon base amount] A solution sample prepared by stirring and mixing approximately 900 mg of the product obtained in Examples 7-12 below (products containing oxyalkylene polymers (Y1-1)-(Y1-4), (Y2-1), and (Y2-2)), approximately 25 mg of p-dinitrobenzene, and approximately 6 g of deuterated chloroform. 1 1H-NMR was measured, and the amount of reactive silicon groups was calculated using the internal standard method with p-dinitrobenzene.

[0096] [Reactive silicon group introduction rate] The rate of reactive silicon group introduction [%] was calculated using the following formula. Reactive silicon group introduction rate = (Amount of reactive silicon groups / Amount of carbon-carbon unsaturated groups) × 100 (b) In formula (b) above, the amount of reactive silicon group and the amount of carbon-carbon unsaturated group were obtained by the same method as described for [amount of reactive silicon group] and [amount of carbon-carbon unsaturated group].

[0097] [Propenyl base] The propenyl group amount [mmol / g] is determined by the same method as described above for the [reactive silicon group amount]. 1 1H-NMR measurements were performed, and the results were calculated using the internal standard method with p-dinitrobenzene.

[0098] [Propenyl group ratio] The propenyl group content [mol%] was calculated from the above carbon-carbon unsaturated group content and propenyl group content using the following formula (c). Propenyl group ratio = Amount of propenyl groups ÷ Amount of carbon-carbon unsaturated groups × 100 (c)

[0099] [Example 1] 4000 g of polyoxypropylene glycol (oxyalkylene polymer (A-1), a polymer obtained by ring-opening polymerization of propylene oxide in the presence of a zinc hexacyanocobaltate complex (hereinafter also called "TBA-DMC catalyst") with t-butanol as a ligand, using propylene glycol (2 hydroxyl groups in one molecule) as an initiator. Hydroxyl value 7.9 mg KOH / g, molecular weight based on hydroxyl value 14200, number average molecular weight 20400, TBA-DMC catalyst content 50 ppm by mass) was charged into the reactor, and after purging with nitrogen, the reactor was dehydrated under reduced pressure of -0.1 MPaG until the water content was 100 ppm by mass or less. Next, nitrogen was used to reduce the reactor pressure to atmospheric pressure. Then, 84.0 g of 1-vinyl-3,4-epoxycyclohexane (manufactured by Daicel Corporation, trade name: Celoxide 2000) (1.20 moles per mole of hydroxyl groups of oxyalkylene polymer (A-1)) was sequentially added as the alicyclic epoxy compound (B) over 3.5 hours at 140°C, followed by a reaction for 9 hours. After that, the mixture was defoliated at 140°C and -0.1 MPaG for 1 hour to remove the unreacted alicyclic epoxy compound, yielding a product containing an oxyalkylene polymer (X1-1) having vinyl groups at its terminals.

[0100] [Example 2] 4000 g of polyoxypropylene monool (oxyalkylene polymer (A-2), obtained by ring-opening polymerization of propylene oxide in the presence of a TBA-DMC catalyst using n-butanol (1 hydroxyl group per molecule) as an initiator; hydroxyl value 11.5 mg KOH / g, molecular weight based on hydroxyl value 4880, number average molecular weight 7731, TBA-DMC catalyst content 50 ppm by mass) was charged into the reactor, and after nitrogen purging, the reactor was dehydrated under reduced pressure of -0.1 MPaG until the water content was 100 ppm by mass or less. Next, a product containing an oxyalkylene polymer (X1-2) having vinyl groups at its terminals was obtained in the same manner as in Example 1, except that oxyalkylene polymer (A-2) was used instead of the raw material oxyalkylene polymer (A-1).

[0101] [Example 3] 4000 g of polyoxypropylene glycol (oxyalkylene polymer (A-3), obtained by ring-opening polymerization of propylene oxide in the presence of a TBA-DMC catalyst using sorbitol (6 hydroxyl groups per molecule) as an initiator; hydroxyl value 8.2 mg KOH / g, molecular weight based on hydroxyl value 41050, number average molecular weight 34600, TBA-DMC catalyst content 100 ppm by mass) was charged into the reactor, and after nitrogen purging, dehydration was performed under reduced pressure of -0.1 MPaG until the water content was 100 ppm by mass or less. Next, using oxyalkylene polymer (A-3) instead of the starting material oxyalkylene polymer (A-1), a product containing oxyalkylene polymer (X1-3) having vinyl groups at the terminals was obtained in the same manner as in Example 1, except that 1.0 mole of celloxide 2000 was added sequentially at 140°C for 10 hours per mole of hydroxyl groups of polyoxypropylene polyol, followed by a reaction for 1 hour.

[0102] [Example 4] In the same manner as in Example 1, a dehydrated oxyalkylene polymer (A-1) was obtained. Subsequently, 4000 g of the obtained oxyalkylene polymer (A-1) was charged into a reactor, and a 28% by mass sodium methoxide (NaOMe) methanol solution was added so that 1.05 moles of NaOMe were added per mole of hydroxyl groups of the oxyalkylene polymer (A-1). The reaction was carried out at 130°C for 4 hours under a nitrogen atmosphere, and then defoliated at 130°C for 20 hours under reduced pressure to remove methanol by distillation, thereby converting the hydroxyl groups of the oxyalkylene polymer (A-1) to metal alkoxides. Next, an excess amount of allyl chloride was added relative to the number of terminals converted to metal alkoxides, and the mixture was reacted at 85°C for 4 hours to obtain a crude oxyalkylene polymer (X1-4) with allyloxy groups at the terminals. Subsequently, the mixture was defoliated under reduced pressure of -0.1 MPaG at 85°C for 2 hours to remove unreacted allyl chloride. To 100 parts by mass of this crude product, 0.3 parts by mass of surfactant and 5 parts by mass of water were added, and the mixture was stirred and mixed under a nitrogen atmosphere at a liquid temperature of 80°C to extract the by-product salt, NaCl, with water. Subsequently, the mixture was held at a liquid temperature of 80°C under a nitrogen atmosphere for 5 hours to evaporate the water and precipitate NaCl crystals. The precipitated NaCl crystals were filtered, and the resulting filtrate was dehydrated under reduced pressure to obtain a product containing an oxyalkylene polymer (X1-4) having allyloxy groups at its termini.

[0103] [Example 5] In the same manner as in Example 1, a dehydrated oxyalkylene polymer (A-1) was obtained. Subsequently, 4000 g of the obtained oxyalkylene polymer (A-1) was charged into a reactor, and 72.6 g of Celoxide 2000 (1.03 moles per mole of hydroxyl groups of oxyalkylene polymer (A-1)) was added sequentially over 5.5 hours at 140°C under a nitrogen atmosphere, followed by a reaction for 7 hours to obtain an oxyalkylene polymer (X1-5) having vinyl groups at its ends. Next, a 28% by mass sodium methoxide (NaOMe) methanol solution was added to the oxyalkylene polymer (A-1) at a ratio of 1.05 moles of NaOMe per mole of hydroxyl groups. The mixture was reacted under a nitrogen atmosphere at 130°C for 4 hours, and then defoliated under reduced pressure of -0.1 MPaG at 130°C for 20 hours to remove methanol by distillation, converting the hydroxyl groups of the oxyalkylene polymer (X1-5) to metal alkoxides. Next, an excess amount of allyl chloride was added to the metal alkoxide-converted end of the oxyalkylene polymer (X1-5) and reacted at 85°C for 12 hours. Then, defoliation was carried out at 85°C for 2 hours under reduced pressure of -0.1 MPaG to remove unreacted allyl chloride. Next, in the same manner as in Example 4, the by-product salt NaCl was extracted with water and filtered to obtain a product containing an oxyalkylene polymer (X2-1) in which the hydroxyl groups were converted to allyloxy groups and which had two carbon-carbon unsaturated groups at its terminal ends.

[0104] [Example 6] In the same manner as in Example 1, a dehydrated oxyalkylene polymer (A-1) was obtained. Subsequently, 4000 g of the obtained oxyalkylene polymer (A-1) was charged into a reactor, and 1.15 moles of NaOMe were added per mole of hydroxyl groups of the oxyalkylene polymer (A-1). The reaction was carried out at 130°C for 4 hours under a nitrogen atmosphere, and then defoliated at 130°C for 20 hours under reduced pressure of -0.1 MPaG to remove methanol by distillation, converting the hydroxyl groups of the oxyalkylene polymer (A-1) to metal alkoxides. Next, 1.05 moles of allyl glycidyl ether were added per mole of the metal alkoxide-converted terminals of the oxyalkylene polymer (A-1), and the mixture was reacted at 130°C for 2 hours. Furthermore, 0.28 moles of sodium methoxide were added per mole of the metal alkoxide-converted terminals of the oxyalkylene polymer (A-1), and methanol was removed by distillation under reduced pressure. Subsequently, an excess amount of allyl chloride was added to the metal alkoxide-converted terminals of the oxyalkylene polymer (A-1), and the mixture was reacted to obtain the crude product of oxyalkylene polymer (X2-2), which has allyloxy groups at the terminals. After that, the mixture was defoliated under reduced pressure of -0.1 MPaG at 85°C for 2 hours to remove unreacted allyl chloride. Next, in the same manner as in Example 4, the by-product salt NaCl was extracted with water and filtered to obtain a product containing an oxyalkylene polymer (X2-2) having two carbon-carbon unsaturated groups at its termini.

[0105] Table 1 shows the average number of hydroxyl groups, molecular weight based on hydroxyl value, and the amount of aliphatic hydrocarbon rings added during the production of oxyalkylene polymers (X1-1) to (X1-4), (X2-1), and (X2-2) (referring to the amount of alicyclic epoxy compound (B) added per mole of hydroxyl groups in oxyalkylene polymers (A-1) to (A-3)), as well as the amount of carbon-carbon unsaturated groups. Examples 1 to 3 and 5 are examples, while examples 4 and 6 are comparative examples. Furthermore, the "Average Number of Hydroxyl Groups" in Table 1 lists the number of hydroxyl groups of the initiators (propylene glycol, n-butyl alcohol, and sorbitol) used in the synthesis of oxyalkylene polymer (A), and these values ​​directly represent the average number of hydroxyl groups of oxyalkylene polymer (A).

[0106] [Table 1]

[0107] [Example 7] 300 g of the oxyalkylene polymer (X1-1) obtained in Example 1 was charged into a reactor, and 10.6 g of dimethoxymethylsilane (1.85 moles per mole of carbon-carbon unsaturated groups) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the reaction was carried out at 85°C for 5 hours. Subsequently, the unreacted dimethoxymethylsilane was removed by defoliation at 85°C for 2 hours under reduced pressure of -0.1 MPaG, and a product containing the oxyalkylene polymer (Y1-1) was obtained in which the vinyl groups were converted to -CH2CH2-Si(OCH3)2CH3.

[0108] [Example 8] 300 g of the oxyalkylene polymer (X1-2) obtained in Example 2 was charged into a reactor, and 11.5 g of dimethoxymethylsilane (1.50 moles per mole of carbon-carbon unsaturated groups) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the reaction was carried out at 85°C for 5 hours. Subsequently, the unreacted dimethoxymethylsilane was removed by defoliation at 85°C for 2 hours under reduced pressure of -0.1 MPaG, and a product containing the oxyalkylene polymer (Y1-2) was obtained in which the vinyl groups were converted to -CH2CH2-Si(OCH3)2CH3.

[0109] [Example 9] 300 g of the oxyalkylene polymer (X1-3) obtained in Example 3 was charged into a reactor, and 7.6 g of dimethoxymethylsilane (1.50 moles per mole of allyl group) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the reaction was carried out at 85°C for 5 hours. Subsequently, the unreacted dimethoxymethylsilane was removed by defoliation at 85°C for 2 hours under reduced pressure of -0.1 MPaG, and a product containing the oxyalkylene polymer (Y1-3) was obtained in which the vinyl group was converted to -CH2CH2-Si(OCH3)2CH3.

[0110] [Example 10] 300 g of the oxyalkylene polymer (X1-4) obtained in Example 4 was charged into a round-bottom flask, and 8.8 g of dimethoxymethylsilane (1.85 moles per mole of allyl group) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the mixture was reacted at 85°C for 5 hours. Subsequently, the mixture was defoliated at 85°C for 2 hours under reduced pressure of -0.1 MPaG to remove unreacted dimethoxymethylsilane, and a product containing the oxyalkylene polymer (Y1-4) was obtained, in which the allyloxy group was converted to -O-CH2CH2CH2-Si(OCH3)2CH3.

[0111] [Example 11] 300 g of oxyalkylene polymer (X2-1) was charged into a reactor, and 8.4 g of dimethoxymethylsilane (1.00 mole per mole of carbon-carbon unsaturated group) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the reaction was carried out at 85°C for 5 hours. Subsequently, the unreacted dimethoxymethylsilane was removed by defoliation at 85°C for 2 hours under reduced pressure of -0.1 MPaG, and a product containing the converted oxyalkylene polymer (Y2-1) was obtained, in which the oxyallyl group was converted to -O-CH2CH2CH2-Si(OCH3)2CH3.

[0112] [Example 12] 300 g of oxyalkylene polymer (X2-2) was charged into a reactor, and 8.4 g of dimethoxymethylsilane (1.00 mol per mole of carbon-carbon unsaturated groups) was added in the presence of hexahydrate chlorplatinum(IV) chloride, and the reaction was carried out at 85°C for 5 hours. Subsequently, the unreacted dimethoxymethylsilane was removed by defoliation at 85°C for 2 hours under reduced pressure of -0.1 MPaG, and a product containing the converted oxyalkylene polymer (Y2-2) was obtained, in which the oxyallyl groups were converted to -O-CH2CH2CH2-Si(OCH3)2CH3.

[0113] Table 2 shows the amount of reactive silicon groups, the rate of reactive silicon group introduction, the amount of propenyl groups, and the propenyl group ratio for the oxyalkylene polymers (Y1-1) to (Y1-4), (Y2-1), and (Y2-2) in Examples 7 to 12. Examples 7 to 9 and 11 are examples, while Examples 10 and 12 are comparative examples.

[0114] [Table 2]

[0115] As shown in Table 2, the oxyalkylene polymers (Y1-1) to (Y1-3) produced using oxyalkylene polymers (X1-1) to (X1-3) have a lower propenyl group ratio and a higher rate of reactive silicon group introduction compared to the oxyalkylene polymer (Y1-4) produced using oxyalkylene polymer (X1-4). Similarly, the oxyalkylene polymer (Y2-1) produced using oxyalkylene polymer (X2-1) has a lower propenyl group ratio and a higher rate of reactive silicon group introduction compared to the oxyalkylene polymer (Y2-2) produced using oxyalkylene polymer (X2-2). In the oxyalkylene polymers (Y1-4) and (Y2-2) produced using oxyalkylene polymers (X1-4) and (X2-2) having allyloxy groups as terminal carbon-carbon unsaturated groups, it is thought that a portion of the double bond of the allyl group was transferred, resulting in a higher propenyl group ratio and a lower rate of reactive silicon group introduction.

Claims

1. A method for producing an oxyalkylene polymer (X), comprising reacting a hydroxyl group of an oxyalkylene polymer (A) with an epoxy group of an alicyclic epoxy compound (B) in the presence of a complex metal cyanide catalyst, The oxyalkylene polymer (A) has at least one hydroxyl group at one of its terminals, The alicyclic epoxy compound (B) has a substituent (a) having a carbon-carbon unsaturated group (excluding allyl groups), A method for producing the oxyalkylene polymer (X), wherein the oxyalkylene polymer (X) has a carbon-carbon unsaturated group derived from the substituent (a) at its terminal end.

2. A method for producing an oxyalkylene polymer (X) according to claim 1, wherein the number average molecular weight of the oxyalkylene polymer (A) is 2,000 to 50,000.

3. A method for producing an oxyalkylene polymer (X) according to claim 1, wherein the average number of hydroxyl groups per molecule of the oxyalkylene polymer (A) is 1 to 8.

4. The method for producing the oxyalkylene polymer (X) according to claim 1, wherein the oxyalkylene polymer (A) includes a structural unit derived from propylene oxide.

5. The oxyalkylene polymer (A) further comprises constituent units derived from ethylene oxide, A method for producing an oxyalkylene polymer (X) according to claim 4, wherein the ratio of the constituent units derived from ethylene oxide to all constituent units of the oxyalkylene polymer (A) is 1 to 30% by mass.

6. The method for producing an oxyalkylene polymer (X) according to claim 1, wherein the alicyclic skeleton of the alicyclic epoxy compound (B) is a monocyclic or polycyclic structure with 3 to 12 ring-forming carbon atoms.

7. The method for producing an oxyalkylene polymer (X) according to claim 1, wherein the alicyclic epoxy compound (B) is a compound represented by the following formula (i). 【Chemistry 1】 (In formula (i), R １ ~R ４ One selected from represents the substituent (a), R other than substituent (a) １ ~R ４ (This represents a hydrogen atom.)

8. The aforementioned R ２ or R ３ The method for producing the oxyalkylene polymer (X) according to claim 7, wherein the substituent (a) is the substituent (a).

9. The method for producing an oxyalkylene polymer (X) according to claim 1, wherein the substituent (a) is at least one selected from the group consisting of a vinyl group, a vinyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a propargyl group.

10. The method for producing an oxyalkylene polymer (X) according to claim 1, wherein the alicyclic epoxy compound (B) is at least one selected from the group consisting of 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

11. A method for producing an oxyalkylene polymer (Y), comprising reacting the carbon-carbon unsaturated group having a terminal of an oxyalkylene polymer (X) obtained by the production method described in claim 1 with a hydrosilane compound (C) having a hydrolyzable group represented by the following formula (ii), The oxyalkylene polymer (Y) is having a reactive silicon group at its terminal end, and the method for producing the oxyalkylene polymer (Y) is also described. -SiX ｎ R ３－ｎ (ii) (In formula (ii), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer between 1 and 3. When n is 1, the multiple R values ​​may be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different. However, R excludes hydrolyzable groups.

12. An oxyalkylene polymer (Y1) having a reactive silicon group at the terminal end, with a group represented by the following formula (2) at the terminal end. 【Chemistry 2】 (In formula (2), R ５ ~R ８ One selected from them is a group represented by the following formula (iii), R is not a group represented by the above formula (iii). ５ ~R ８ This represents a hydrogen atom, *b represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (Y1). -R ９ -SiX ｎ R ３－ｎ (iii) (In formula (iii), R ９ This represents a -CH2CH2- group, X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer between 1 and 3. When n is 1, the multiple R values ​​may be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different.

13. The hydroxyl group of the group represented by the following formula (1) at the terminal end of the oxyalkylene polymer (X) obtained by the manufacturing method described in claim 7 is converted to a metal alkoxide with an alkali metal alkoxide, and then reacted with an organic halogen compound having an unsaturated bond at the terminal to obtain an oxyalkylene polymer (X2) in which the substituent (b) has a carbon-carbon unsaturated group. A method for producing an oxyalkylene polymer (Y2), comprising reacting the carbon-carbon unsaturated group of substituent (a) and the carbon-carbon unsaturated group of substituent (b) in the oxyalkylene polymer (X2) with a hydrolyzable group (C) represented by the following formula (ii), A method for producing the oxyalkylene polymer (Y2), wherein the oxyalkylene polymer (Y2) has two reactive silicon groups at its terminal ends. 【Transformation 3】 (In formula (1), R １ ~R ４ One selected from represents the substituent (a), R other than substituent (a) １ ~R ４ This represents a hydrogen atom, *a represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (X). -SiX ｎ R ３－ｎ (ii) (In formula (ii), X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer between 1 and 3. When n is 1, the multiple R values ​​may be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different. However, R excludes hydrolyzable groups.

14. An oxyalkylene polymer (Y2) having two reactive silicon groups at its termini, with a group represented by the following formula (3) at its termini. 【Chemistry 4】 (In formula (3), R ５ ~R ８ One of the selected bases is represented by the following formula (iii): R is not a group represented by the above formula (iii). ５ ~R ８ This represents a hydrogen atom, R １０ This represents the -O-CH2CH2CH2- group, X represents a hydrolyzable group or a hydroxyl group, R represents a monovalent organic group with 1 to 20 carbon atoms. n is an integer between 1 and 3. When n is 1, the multiple R values ​​may be the same or different. If n is 2 or 3, the multiple X values ​​may be the same or different. However, R excludes hydrolyzable groups. *c represents the bond position to the oxyalkylene chain of the oxyalkylene polymer (Y2). -R ９ -SiX ｎ R ３－ｎ (iii) (In formula (iii), R ９ This represents a -CH2CH2- group, X, R, and n are defined as in equation (3).

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