Method for producing polyoxyalkylene-based polymer

Abstract

A polyoxyalkylene-based polymer (A) having a carbon-carbon unsaturated bond is produced by adding an epoxy compound (D) having a carbon-carbon unsaturated bond but not having an alicyclic structure to a system containing a hydroxyl group-containing polyoxyalkylene-based polymer (B) and a double metal cyanide catalyst (C), and reacting an epoxy group included in the compound (D) and a hydroxyl group included in the polymer (B) at 115-160°C.

Description

Method for Producing Polyoxyalkylene Polymer

[0001] The present invention relates to a method for producing a polyoxyalkylene polymer having a carbon-carbon unsaturated bond or a reactive silicon group.

[0002] It is known that a polyoxyalkylene polymer having a reactive silicon group crosslinks through formation of siloxane bonds accompanied by hydrolysis reaction and condensation reaction of reactive silicon groups in the presence of moisture, to give a rubber-like cured product. Such polymers have already been industrially produced and are widely used in applications such as adhesives, sealing agents, coating agents, paints, and pressure-sensitive adhesives.

[0003] As one method for producing such a polymer having a reactive silicon group, a method of introducing a reactive silicon group into a polymer by causing an addition reaction of a reactive silicon group-containing hydrosilane compound to a polymer having a carbon-carbon unsaturated bond is known. Therefore, a polymer having a carbon-carbon unsaturated bond is important as an intermediate when producing a polymer having a reactive silicon group.

[0004] As one method for producing a polymer having a carbon-carbon unsaturated bond, it is known that a carbon-carbon unsaturated bond is introduced into a polymer by allowing an alkali metal salt to act on a polymer having a hydroxyl group to alkoxylate the hydroxyl group, then reacting the resulting product with an epoxy compound having a carbon-carbon unsaturated bond such as allyl glycidyl ether or a halogenated organic compound having a carbon-carbon unsaturated bond such as allyl chloride (see Patent Document 1).

[0005] As another method, a method of introducing a carbon-carbon unsaturated bond into a polymer is known, in which without performing alkoxylation using an alkali metal salt, an epoxy compound having a carbon-carbon unsaturated bond is added to a system containing a polymer having a hydroxyl group and a double metal cyanide complex catalyst and allowed to react, to introduce a carbon-carbon unsaturated bond into the polymer (see Patent Documents 2 to 3).

[0006] Furthermore, Patent Document 4 discloses a method for introducing carbon-carbon unsaturated bonds into a polymer by reacting a polymer having hydroxyl groups with an alicyclic epoxy compound having carbon-carbon unsaturated bonds other than allyl groups in the presence of a complex metal cyanide catalyst, without performing alkoxylation using an alkali metal salt.

[0007] International Publication No. 2013 / 180203, Japanese Patent Publication No. Hei 3-79627, Japanese Patent Publication No. 2001-55438, Japanese Patent Publication No. 2023-167514

[0008] In the method described in Patent Document 1, when hydroxyl groups of a polymer are reacted with an alkali metal salt to alkoxylate them, byproducts such as alcohols must be removed by vacuum defloration or other means in order to ensure the reaction proceeds efficiently. Therefore, this is a complicated industrial process, and there is a need to simplify it.

[0009] On the other hand, methods using complex metal cyanide catalysts instead of alkali metal salts, as described in Patent Documents 2 to 4, have the advantage that no by-products like those mentioned above are generated and do not need to be removed. However, there is a problem in that the epoxy compound reacts unevenly with some polymer molecules, making it difficult to uniformly introduce carbon-carbon unsaturated bonds throughout the polymer (see paragraph 0078 of Patent Document 1).

[0010] Furthermore, Patent Document 4 requires the use of special compounds having an alicyclic structure, such as 1-vinyl-3,4-epoxycyclohexane, as the epoxy compound having a carbon-carbon unsaturated bond, which limits the structure of the resulting carbon-carbon unsaturated bond-containing polymer.

[0011] In view of the above situation, the present invention aims to provide a method for producing a polyoxyalkylene polymer having carbon-carbon unsaturated bonds by reacting a hydroxyl group-containing polyoxyalkylene polymer with an epoxy compound containing carbon-carbon unsaturated bonds that does not have an alicyclic structure, and which allows for the uniform introduction of carbon-carbon unsaturated bonds into the polymer through a simple process.

[0012] The inventors of this invention discovered that when adding an epoxy compound having carbon-carbon unsaturated bonds to a system containing a polymer having hydroxyl groups and a complex metal cyanide catalyst, without alkoxyling the hydroxyl groups of the polymer, and carrying out the reaction at a specific temperature, the bias in which the epoxy compound reacts with the polymer molecules is reduced, and carbon-carbon unsaturated bonds can be introduced to the polymer relatively uniformly, leading to the present invention.

[0013] In other words, the present invention relates to a method for producing a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds, comprising the steps of adding an epoxy compound (D) having carbon-carbon unsaturated bonds and not having an alicyclic structure, without alkoxylation of the hydroxyl groups of polymer (B) to a system containing a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide complex catalyst (C), and reacting the hydroxyl groups of polymer (B) with the epoxy groups of compound (D) at 115 to 160°C. The present invention also relates to a method for producing a reactive silicon group-containing polyoxyalkylene polymer (G), comprising the steps of obtaining a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds by the above production method, and hydrosilylation reacting polymer (A) with a reactive silicon group-containing hydrosilane compound (F).

[0014] According to the present invention, in a method for producing a polyoxyalkylene polymer having carbon-carbon unsaturated bonds by reacting a hydroxyl group-containing polyoxyalkylene polymer with an epoxy compound containing carbon-carbon unsaturated bonds that does not have an alicyclic structure, it is possible to provide a production method that allows for the uniform introduction of carbon-carbon unsaturated bonds into the polymer through a simple process. The produced polyoxyalkylene polymer having carbon-carbon unsaturated bonds has little bias in the distribution of carbon-carbon unsaturated bonds and can have carbon-carbon unsaturated bonds relatively uniformly.

[0015] According to the present invention, since it is not necessary to remove by-products generated in the conventional manufacturing process, including alkoxylation, by vacuum defloration or the like, polyoxyalkylene polymers having carbon-carbon unsaturated bonds can be produced by a simple process.

[0016] Furthermore, since a compound without an alicyclic structure is used as the epoxy compound containing carbon-carbon unsaturated bonds, it is possible to produce a carbon-carbon unsaturated bond-containing polyoxyalkylene polymer that does not have an alicyclic structure.

[0017] According to the present invention, a method for producing a polyoxyalkylene polymer having reactive silicon is available, which allows for the uniform introduction of reactive silicon through a simple process. The produced polyoxyalkylene polymer having reactive silicon exhibits less bias in the distribution of reactive silicon and can have relatively uniform reactive silicon content.

[0018] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below, and various modifications are possible within the scope defined in the claims. Furthermore, the configurations described below can be combined in any way, and such combinations may also constitute an embodiment of the present invention.

[0019] [First Embodiment] The first embodiment of the present invention relates to a method for producing a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds by adding an epoxy compound (D) that does not have an alicyclic structure and has carbon-carbon unsaturated bonds, without alkoxyling the hydroxyl groups of polymer (B), to a system containing a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide complex catalyst (C), and reacting the two. First, each component will be described.

[0020] [Polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds] Polymer (A) has a polyoxyalkylene polymer skeleton as its polymer backbone. A polyoxyalkylene polymer is one that has a polymer skeleton composed of oxyalkylene repeating units. The polymer skeleton may be linear or branched.

[0021] It is preferable that the polymer skeleton is a polymer skeleton composed only of oxyalkylene repeating units, or a polymer skeleton that includes, in addition to oxyalkylene repeating units, a structure derived from an initiator used during polymerization and is composed only of these. Here, the oxyalkylene repeating unit refers to a repeating unit that constitutes a polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0022] The polyoxyalkylene-based polymer is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers. In particular, polyoxypropylene-based polymers are preferred.

[0023] The carbon-carbon unsaturated bond contained in the polymer (A) may be either a carbon-carbon double bond or a carbon-carbon triple bond, but a carbon-carbon double bond is preferred from the perspective of the ease of the introduction reaction into the polymer.

[0024] The structure of the carbon-carbon double bond contained in the polymer (A) is not particularly limited, but from the perspective of reactivity with the hydrosilane compound (F) described below, it is particularly preferably represented by the following formula (1). -R １ -C(R ２ )=CH ２   (1)

[0025] In formula (1), R １ represents a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may optionally contain an oxygen atom. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and even more preferably 1. R １ is preferably a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a direct bond, -CH ２ -, or -CH ２ CH ２ -, even more preferably a direct bond or -CH ２ -, and particularly preferably -CH ２ -. In addition, when multiple R groups are present in the polymer １They may be the same or they may be different.

[0026] In formula (1), R ２ This represents hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted C7-C10 aralkyl group. The alkyl group preferably has 1-8 carbon atoms, more preferably 1-6, even more preferably 1-3, and particularly preferably 1 or 2. The alkyl group preferably does not contain an alicyclic structure. The aryl group preferably has 6-8 carbon atoms, more preferably 6-7. The aralkyl group is more preferably 7-8 carbon atoms.

[0027] When the alkyl group, aryl group, or aralkyl group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0028] R ２ Specific examples include hydrogen, alkyl groups such as methyl, ethyl, propyl, and butyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. Hydrogen or alkyl groups are particularly preferred, hydrogen, methyl, or ethyl groups are more preferred, and hydrogen or methyl groups are even more preferred. In addition, multiple R groups present in the polymer are also considered. ２ They may be the same or they may be different.

[0029] In formula (1), according to a particularly preferred embodiment, R １ ga-CH ２ - and R ２ It is either a hydrogen atom or a methyl group.

[0030] The number of carbon-carbon unsaturated bonds per molecule of polyoxyalkylene polymer (A) is determined by the number of hydroxyl groups present in the hydroxyl group-containing polyoxyalkylene polymer (B). When polymer (B) having one hydroxyl group is used, the number of carbon-carbon unsaturated bonds per molecule of polymer (A) is preferably at least one on average, and more preferably greater than 1.0. The average number of carbon-carbon unsaturated bonds per molecule of polymer (A) is more preferably 1.2 or more, even more preferably 1.4 or more, and particularly preferably 1.5 or more. There is no particular upper limit to this average number, but it is preferably 30 or less, more preferably 10 or less, and even more preferably 5 or less.

[0031] When a polymer (B) having two hydroxyl groups is used, the number of carbon-carbon unsaturated bonds per molecule of the polyoxyalkylene polymer (A) is preferably at least 2 on average, and more preferably greater than 2.0. This facilitates the formation of crosslinked structures between polymer molecules and the formation of a rubbery cured product with good physical properties when synthesizing and curing the reactive silicon group-containing polyoxyalkylene polymer (G). The average number of carbon-carbon unsaturated bonds per molecule of polymer (A) is more preferably 2.4 or more, even more preferably 2.8 or more, and particularly preferably 3.0 or more. There is no particular upper limit to this average number, but it is preferably 60 or less, more preferably 20 or less, and even more preferably 10 or less.

[0032] When a polymer (B) having three hydroxyl groups is used, the number of carbon-carbon unsaturated bonds per molecule of the polyoxyalkylene polymer (A) is preferably at least 3 on average, and more preferably greater than 3.0. This facilitates the formation of crosslinked structures between polymer molecules and the formation of a rubbery cured product with good physical properties when synthesizing and curing the reactive silicon group-containing polyoxyalkylene polymer (G). The average number of carbon-carbon unsaturated bonds per molecule of polymer (A) is more preferably 3.6 or more, even more preferably 4.2 or more, and particularly preferably 4.5 or more. There is no particular upper limit to this average number, but it is preferably 90 or less, more preferably 30 or less, and even more preferably 15 or less.

[0033] The carbon-carbon unsaturated bonds are preferably bonded to the ends of the polymer skeleton of the polyoxyalkylene polymer (A). According to the manufacturing method of this disclosure, one or more carbon-carbon unsaturated bonds can be introduced to one end of the polymer skeleton. The average number of carbon-carbon unsaturated bonds per end of the polymer skeleton of polymer (A) is preferably 1.0 or more, more preferably 1.1 to 30, even more preferably 1.2 to 10, even more preferably 1.5 to 7, and particularly preferably 1.7 to 5.

[0034] It is preferable that a carbon-carbon unsaturated bond-containing structure represented by the following formula (2) is bonded to the ends of the polymer backbone of polymer (A).

[0035]

[0036] In formula (2), R ２ This is the same as defined in equation (1). In equation (2), R ３ R represents a divalent hydrocarbon group having 1 to 6 carbon atoms, which may be directly bonded or have an oxygen atom. The number of carbon atoms in the hydrocarbon group is preferably 1 to 4, more preferably 1 to 2, and even more preferably 2. ３ is, -CH ２ OCH ２ -ien-CH ２ O-, -CH ２- is preferable, -CH ２ OCH ２ - is particularly preferable. Also, there are multiple R ３ They may be the same or they may be different.

[0037] In formula (2), according to a particularly preferred embodiment, R ２ is a hydrogen or methyl group, R ３ ga-CH ２ OCH ２ - is the case.

[0038] In equation (2), n is an integer greater than or equal to 1. There is no particular upper limit, but for example, it may be 50 or less, 30 or less, 20 or less, or 10 or less. However, the value of n is not limited to one value, and may be a mixture of multiple values.

[0039] When multiple values ​​are present for the value of n, the average number of n per structure represented by equation (2) is preferably 0.1 or greater, more preferably 0.5 or greater, even more preferably 1.0 or greater, and particularly preferably 1.5 or greater. The upper limit of the average number of n is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less.

[0040] The average number of structures represented by formula (2) contained in one molecule of polymer (A) is preferably 0.5 or more, more preferably 1 or more. Furthermore, it is preferably 4 or less, and more preferably 3 or less.

[0041] The number-average molecular weight of polymer (A), as polystyrene-equivalent molecular weight in GPC, is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 10,000 or more and less than 35,000. When the number-average molecular weight is within the above range, polymer (A) can have an easy-to-handle viscosity and good workability while keeping manufacturing costs within a reasonable range.

[0042] The molecular weight distribution (Mw / Mn) of polymer (A) is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less. The molecular weight distribution of the polymer can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0043] [Hydroxypropyl group-containing polyoxyalkylene polymer (B)] Polyoxyalkylene polymer (B) preferably has a hydroxyl group bonded to at least one end of the polymer skeleton. The polymer skeleton of polymer (B) is the same as that of polymer (A). Specific examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Polyoxypropylene polymers are particularly preferred.

[0044] A hydroxyl group-containing polyoxyalkylene polymer (B) can be synthesized by polymerizing an alkylene oxide compound (E) onto a hydroxyl group-containing initiator using conventionally known methods. Typically, the number of hydroxyl groups in polymer (B) is determined by the number of hydroxyl groups in the initiator.

[0045] While there are no particular limitations on initiators having hydroxyl groups, examples of initiators having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, low molecular weight polyoxypropylenediol, low molecular weight polyoxypropylenetriol, glycerin, trimethylolpropane, triethylolethane, sorbitol, pentaerythritol, and the like.

[0046] As initiators having one hydroxyl group, monohydric alcohols can be used, such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and low molecular weight polyoxypropylene monoalkyl ethers.

[0047] The alkylene oxide compound (E) is not particularly limited, but examples include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and α-methylstyrene oxide. Among these, alkylene oxides having 2 to 4 carbon atoms are preferred, and propylene oxide is particularly preferred.

[0048] The number-average molecular weight of polymer (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 10,000 or more and less than 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within the above range, polymer (A) with easy-to-handle viscosity and excellent workability can be easily obtained while keeping manufacturing costs within a reasonable range.

[0049] The molecular weight distribution (Mw / Mn) of polymer (B) is not particularly limited, but a narrow distribution is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0050] The polymerization method for producing polymer (B) is not particularly limited and includes, for example, polymerization methods using alkaline catalysts such as KOH, polymerization methods using transition metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrin, polymerization methods using complex metal cyanide complex catalysts, polymerization methods using catalysts consisting of polyphosphazene salts, and polymerization methods using catalysts consisting of phosphazene compounds.

[0051] In particular, polymerization methods using complex metal cyanide catalysts are preferred because they yield polymers with a small molecular weight distribution (Mw / Mn) and allow the polymerization reaction and the reaction between the polymer (B) and the epoxy compound (D) to be carried out continuously in the same system.

[0052] Polymerization reactions are preferably carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it does not contain active hydrogen and is inert to polymerization. Examples include aromatic compounds such as benzene, monochlorobenzene, toluene, ethylbenzene, styrene, and o-, m-, p-xylene; heterocyclic compounds such as tetrahydrofuran, dioxane, furan, and pyran; and polar compounds such as linear ethers such as butyl ethyl ether. One organic solvent may be used alone, or two or more may be used in combination. Among these, heterocyclic compounds and linear ethers are preferred, tetrahydrofuran, dioxane, and butyl ethyl ether are more preferred, and tetrahydrofuran is particularly preferred.

[0053] [Complex Metal Cyanide Catalyst (C)] The complex metal cyanide catalyst (C) is a component used when reacting a hydroxyl group-containing polyoxyalkylene polymer (B) with an epoxy compound (D). In addition, as described above, it can also be used as a polymerization catalyst when producing the hydroxyl group-containing polyoxyalkylene polymer (B).

[0054] The composite metal cyanide complex catalyst (C) can be a conventionally known compound and is not particularly limited, but for example, one represented by the following formula is preferred. Formula: M ｐ {M'[(CN) ｑ (Y) ｒ ] ｓ} ｔ ・y(R)・z(H ２O) In the above formula, M is a metal selected from the group consisting of Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(II), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), and W(VI). M' is a metal selected from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II), V(IV), and V(V). Y is Cl, Br, I, OH, NO, C ２ O ４ SO ４ M is selected from the group consisting of CNS, CNO, NCO, and NCS. R is an organic ligand selected from the group consisting of ketones, ethers, polyethers, aldehydes, esters, alcohols, and amides. M, M', Y, and R may each be one type or two or more types. p, q, r, s, and t are positive numbers that vary depending on the valence and coordination number of the metal, and y and z are positive numbers that vary depending on the coordination number of the metal.

[0055] The composite metal cyanide complex catalyst (C) is preferably a complex containing hexacyanocobaltic acid. Specific examples of such complexes include Zn ３ [Fe(CN)] ６ ] ２ , Zn ３ [Co(CN) ６ ] ２ , Fe[Fe(CN) ６ ], Fe[Co(CN) ６ Examples include ]. In particular, Zn ３ [Co(CN) ６ ] ２ A zinc hexacyanocobaltate complex represented by [formula] is preferred.

[0056] Furthermore, as the complex metal cyanide catalyst (C), a complex in which organic ligands act as ligands is preferred. As organic ligands, alcohols and ethers can be used. Specifically, examples include alcohols such as tert-butyl alcohol, ethanol, sec-butyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-pentyl alcohol, isopentyl alcohol, and isopropyl alcohol; and ethers such as dimethoxyethane, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), dioxane, and polyethers with a number average molecular weight of 150 to 5000 (e.g., polyoxypropylenediol, polyoxypropylenetriol). Of these, ethers are preferred, and glyme is particularly preferred.

[0057] In particular, a zinc hexacyanocobaltate glyme complex is preferred as the composite metal cyanide complex catalyst (C).

[0058] [Epoxy compound having a carbon-carbon unsaturated bond (D)] The epoxy compound having a carbon-carbon unsaturated bond (D) is not particularly limited as long as it has a carbon-carbon unsaturated bond and an epoxy group in one molecule and does not have an alicyclic structure, but for example it can be represented by the following formula (3).

[0059]

[0060] In formula (3), R ２ and R ３ This is the same as the one defined in formula (1) or (2) above.

[0061] The aforementioned alicyclic structure refers to a cyclic hydrocarbon that does not possess aromaticity. The cyclic hydrocarbon may be saturated or unsaturated. Specific examples include structures having cycloalkane rings, cycloalkene rings, bicycloalkane rings, and bicycloalkene rings.

[0062] Since epoxy compound (D) does not have an alicyclic structure, polymers (A) or (G) produced using compound (D) may also lack an alicyclic structure. Because polymers (A) do not have bulky substituents like those found in alicyclic structures near the carbon-carbon unsaturated bond, or polymers (G) near the reactive silicon group, there is an advantage in that the reactivity of the carbon-carbon unsaturated bond or the reactive silicon group is less likely to be inhibited.

[0063] Specific examples of epoxy compound (D) include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, 1,4-cyclopentadiene monoepoxide, 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. From the viewpoint of reaction activity, allyl glycidyl ether is particularly preferred.

[0064] [Method for producing polymer (A)] In the manufacturing method according to this disclosure, first, a system is prepared that includes a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide catalyst (C). The system may optionally contain an organic solvent as described above.

[0065] The system may be prepared by adding a complex metal cyanide catalyst (C) to a hydroxyl group-containing polyoxyalkylene polymer (B) that has been prepared or obtained separately. However, it is preferable that the system includes a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide catalyst (C), obtained by polymerizing an alkylene oxide compound (E) in the presence of the complex metal cyanide catalyst (C). This allows the polymerization step and the reaction between polymer (B) and epoxy compound (D) to be carried out continuously in the same system, simplifying the production process of polymer (A) or polymer (G). Such a system may contain the organic solvent used in the polymerization reaction.

[0066] Next, an epoxy compound (D) that does not have an alicyclic structure and has carbon-carbon unsaturated bonds is added to a system containing a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide catalyst (C), and the system is heated to react the hydroxyl groups of polymer (B) with the epoxy groups of compound (D). When epoxy compound (D) is added, the hydroxyl groups of polymer (B) are not alkoxylated and remain in the form of hydroxyl groups.

[0067] In the reaction between polymer (B) and epoxy compound (D), by adjusting the amount of epoxy compound (D) used and the reaction conditions, one or more epoxy compounds (D) can be added to a single hydroxyl group of polymer (B).

[0068] The amount of epoxy compound (D) added can be appropriately set according to the desired amount of carbon-carbon unsaturated bonds introduced. However, to further reduce the bias in the polymer molecules that react with epoxy compound (D), it is preferable to add an amount such that the molar ratio, expressed as the number of moles of epoxy compound (D) / the number of moles of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene polymer (B), is 1.5 to 50. The lower limit may be 2.0 or higher. The upper limit may be 40 or less, 30 or less, 20 or less, 10 or less, or 6 or less.

[0069] The complex metal cyanide catalyst (C) functions as a catalyst and efficiently promotes the reaction between the hydroxyl groups of the polymer (B) and the epoxy groups of the compound (D). According to the manufacturing method of this disclosure, since the complex metal cyanide catalyst (C) is used as the catalyst for the reaction, there is no need to alkoxylate the hydroxyl groups of the polymer (B) as in conventional methods, and as a result, there is an advantage that there is no need to carry out a step to remove by-products generated by alkoxylation.

[0070] In the manufacturing method described herein, no alkali metal salt is added to alkoxylate the hydroxyl groups of polymer (B). Therefore, the pH of the system containing the hydroxyl group-containing polyoxyalkylene polymer (B) and the complex metal cyanide catalyst (C) is relatively low. Specifically, the pH of the system is preferably 9 or less, more preferably 8.5 or less, and even more preferably 8 or less. The lower limit of the pH is not particularly limited, but may be, for example, 5 or more, 6 or more, or 7 or more.

[0071] The amount of the composite metal cyanide complex used in the reaction between the hydroxyl groups of polymer (B) and the epoxy groups of compound (D) is not particularly limited, but is usually preferably 50 ppm by weight or more, more preferably 80 ppm by weight or more, and even more preferably 100 ppm by weight or more relative to polymer (B).

[0072] When a polymerization reaction and a reaction between polymer (B) and compound (D) are carried out consecutively in the same system, the composite metal cyanide complex catalyst (C) used in the polymerization reaction can be used directly in the latter reaction. In this case, it is not necessary to add the composite metal cyanide complex again after the polymerization reaction, either before or during the reaction between polymer (B) and compound (D).

[0073] In the manufacturing method according to this disclosure, the system is heated to 115°C or higher in order to promote the reaction between the hydroxyl groups of polymer (B) and the epoxy groups of compound (D). By proceeding the reaction between polymer (B) and epoxy compound (D) at such a relatively high temperature, the bias in which the epoxy compound (D) reacts with polymer molecules is reduced, and carbon-carbon unsaturated bonds can be introduced to polymer (B) relatively uniformly. Therefore, polymer (A) having carbon-carbon unsaturated bonds relatively uniformly can be obtained. This is presumed to be because raising the reaction temperature promotes the reaction between the hydroxyl groups of polymer (B) and the epoxy groups.

[0074] From the above viewpoint, the heating temperature during the reaction between polymer (B) and compound (D) is preferably 120°C or higher, more preferably 125°C or higher, even more preferably 130°C or higher, and particularly preferably 135°C or higher. It should be noted that Patent Documents 2 and 3 only disclose that the reaction between polymer (B) and compound (D) was carried out at a low temperature of about 90 to 110°C.

[0075] The temperature during the reaction between polymer (B) and epoxy compound (D) is preferably set to 160°C or lower, from the viewpoint of suppressing undesirable side reactions such as the decomposition of polymer (B). The temperature is more preferably 155°C or lower, even more preferably 150°C or lower, even more preferably 145°C or lower, and particularly preferably 140°C or lower.

[0076] The heating may be performed after the entire amount of epoxy compound (D) has been added to the system, but it is preferable to perform the heating while adding the epoxy compound (D) over time. Addition over time means adding the epoxy compound (D) over a certain period of time rather than adding the entire amount at once, and this may be done in installments, continuously, or intermittently. In particular, continuous or intermittent addition is preferred. At this time, it is preferable to maintain an approximately constant rate of addition of epoxy compound (D).

[0077] By reacting polymer (B) with epoxy compound (D) while adding epoxy compound (D) over time, the concentration of unreacted epoxy compound (D) in the system can be reduced. This further reduces the bias in which polymer molecules react with compound (D), and also suppresses the generation of low molecular weight components caused by polymerization of epoxy compound (D) alone.

[0078] When epoxy compound (D) is added over time, the addition rate can be set as appropriate, but it is preferable that the time required to add epoxy compound (D) in an amount equal to the number of moles of hydroxyl groups in polymer (B) (hereinafter sometimes referred to as "T time") is about 3 to 30 minutes. Setting the time to 3 minutes or more makes it easier to achieve the effects of the time-dependent addition described above. More preferably, it is 4 minutes or more. Furthermore, setting the time to 30 minutes or less shortens the reaction time, which is advantageous from the viewpoint of productivity. More preferably, it is 20 minutes or less, and even more preferably 10 minutes or less.

[0079] Furthermore, the "time required to add epoxy compound (D) in an amount equal to the number of moles of hydroxyl groups in polymer (B)" can be calculated as follows. For example, if the molar ratio expressed as the number of moles of epoxy compound (D) / the number of moles of hydroxyl groups in polymer (B) is 5, and the time required to add the entire amount of epoxy compound (D) is 30 minutes, then the "time required to add epoxy compound (D) in an amount equal to the number of moles of hydroxyl groups in polymer (B)" is 30 minutes / 5 = 6 minutes.

[0080] When adding epoxy compound (D) having carbon-carbon unsaturated bonds, it is preferable to add only epoxy compound (D) having carbon-carbon unsaturated bonds and not epoxy compound without carbon-carbon unsaturated bonds, rather than adding a mixture of epoxy compound (D) and epoxy compound without carbon-carbon unsaturated bonds as described in Patent Document 3. This allows the carbon-carbon unsaturated bonds to be introduced concentrated at the ends of the polymer skeleton rather than being introduced as side chains of the polymer skeleton. When adding only epoxy compound (D), a compound that does not polymerize, such as an organic solvent, may be added together with epoxy compound (D).

[0081] The reaction between polymer (B) and epoxy compound (D) is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

[0082] After the addition of epoxy compound (D) is complete, it is preferable to maintain heating for, for example, 10 minutes to 1 hour to complete the reaction.

[0083] If the reaction is carried out in the presence of an organic solvent, the organic solvent may be removed by distillation after the reaction is complete. The complex metal cyanide catalyst (C) may be removed from the polymer (B) using an adsorbent such as aluminum silicate, magnesium silicate, or Celite. Alternatively, the catalyst (C) may be removed by washing with water or an organic solvent.

[0084] In a preferred embodiment of the manufacturing method, an alkylene oxide compound (E) is polymerized in the presence of a complex metal cyanide catalyst (C) to form a hydroxyl group-containing polyoxyalkylene polymer (B), and an epoxy compound (D) is added to the resulting reaction system and heated, thereby allowing the polymerization reaction of the alkylene oxide compound (E) and the reaction between the polymer (B) and the epoxy compound (D) to be carried out continuously in the same system. According to this embodiment, the manufacturing process of polymer (A) or polymer (G) can be simplified.

[0085] In this embodiment, it is preferable to add the epoxy compound (D) after confirming that the polymerization of the alkylene oxide compound (E) is complete. This allows the polymerization reaction and the reaction with the epoxy compound (D) to be separated, and after the formation of the polymer skeleton is complete, carbon-carbon unsaturated bonds can be concentrated and introduced at the ends of the polymer skeleton. The completion of the polymerization reaction can be confirmed by measuring the concentration of the alkylene oxide compound (E) in the reaction solution or by the cessation of the decrease in pressure in the reaction vessel.

[0086] The polymer (A) produced by the manufacturing method according to this disclosure may have hydroxyl groups in addition to carbon-carbon unsaturated bonds, as shown in formula (2) above. The hydroxyl groups of this polymer (A) can be converted to groups without active hydrogen as needed. Known methods can be used for such conversions, and examples include urethane formation using monoisocyanate compounds, etc.; silyl ether formation using silylating agents such as trialkylsilyl chloride and hexamethyldisilazane; esterification using acid anhydrides and acid chlorides, etc.; alkylation using alkyl halides and allyl halides, etc.; ether formation using vinyl ether compounds such as dihydropyran; and t-butyl ether formation using isobutylene. Polymers in which the hydroxyl groups have been converted to groups without active hydrogen are also included in the range of carbon-carbon unsaturated bond-containing polyoxyalkylene polymers (A) according to this disclosure.

[0087] The polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds is not particularly limited in its applications. As described later, it can be suitably used as a raw material for producing reactive silicon group-containing polyoxyalkylene polymer (G). In addition, it can be used as a base polymer for addition-curing type curable compositions utilizing hydrosilylation reactions with polyhydrosilyl compounds or enthiol reactions with polythiol compounds. It can also be used as a macromonomer.

[0088] [Second Aspect] The second aspect of the present invention relates to a method for producing a reactive silicon group-containing polyoxyalkylene polymer (G). First, the polymer (G) will be described.

[0089] [Polyoxyalkylene polymer (G) containing reactive silicon groups] The reactive silicon groups in polymer (G) refer to silicon groups that can form siloxane bonds and bond to each other through hydrolysis and dehydration condensation. Polymer (G) exhibits curability based on dehydration condensation reactions due to the presence of reactive silicon groups.

[0090] A reactive silicon group can be represented, for example, by the following formula (4): -SiR ４ ａ X ３－ａ(4) In formula (4), R ４ R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. ４ If multiple hydrocarbon groups exist, they may be identical or different from one another. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. If the hydrocarbon group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0091] R ４ Examples include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl groups; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl groups; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, toluyl, and 1-naphthyl groups; and aralkyl groups such as benzyl groups. Preferably, the alkyl group is substituted or unsubstituted, more preferably methyl, ethyl, chloromethyl, or methoxymethyl, even more preferably methyl or methoxymethyl, and particularly preferably methyl. ４ For this purpose, only one type of group may be used, or two or more types of groups may be used in combination.

[0092] In formula (4), X represents a hydroxyl group or a hydrolyzable group. If there are multiple Xs, they may be the same or different from each other. Examples of X include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. The aforementioned alkoxy groups may have substituents. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle, methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups are more preferred, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred. Only one type of group may be used as X, or two or more types of groups may be used in combination.

[0093] In formula (4), a is 0, 1, or 2. From the viewpoint of curability and the mechanical properties of the resulting cured product, a is preferably 0 or 1.

[0094] Examples of reactive silicon groups represented by formula (4) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred. From the viewpoint of reactivity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred. From a stability standpoint, methyldimethoxysilyl groups and methyldiethoxysilyl groups are more preferred. Furthermore, methyldimethoxysilyl groups are more preferred because they are easy to manufacture.

[0095] The method for producing polymer (G) according to this disclosure allows for the introduction of a structure having two or more reactive silicon groups into the polymer. Such a structure can be represented, for example, by the following formula (5). That is, polymer (G) may contain a structure represented by the following formula (5).

[0096]

[0097] In formula (5), R ２ , R ３ , and n are the same as those defined in formula (1) or (2) above. R ４ X and a are the same as those defined in formula (4) above.

[0098] The structure represented by formula (5) is preferably bonded to the end of the polymer backbone of polymer (G).

[0099] The average number of structures represented by formula (5) contained in one molecule of polymer (G) is preferably 0.5 or more, more preferably 1 or more. It is also preferably 4 or less, and more preferably 3 or less.

[0100] The hydroxyl group in formula (5) may be converted to a group without active hydrogen by the method described above.

[0101] Polymer (G) is produced by introducing reactive silicon groups into polymer (A), which has relatively uniform carbon-carbon unsaturated bonds. As a result, there is less bias in the distribution of reactive silicon groups, and the reactive silicon groups are relatively uniform. Consequently, the physical properties of the cured product obtained by curing polymer (G) can be improved.

[0102] The polymer skeleton of polymer (G) having reactive silicon groups is the same as that of polymer (A). Specific examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Polyoxypropylene polymers are particularly preferred.

[0103] The number-average molecular weight of polymer (G) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 10,000 or more and less than 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within the above range, the polymer (G) can have an easy-to-handle viscosity and good workability while keeping manufacturing costs within a reasonable range.

[0104] The molecular weight distribution (Mw / Mn) of the polymer (G) is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0105] [Method for producing polymer (G)] The reactive silicon group-containing polyoxyalkylene polymer (G) can be produced by first producing a polymer (A) having carbon-carbon unsaturated bonds by the process described above, and then hydrosilylating polymer (A) with a reactive silicon group-containing hydrosilane compound (F).

[0106] A reactive silicon group-containing hydrosilane compound (F) can be represented, for example, by the following formula (6): H-SiR ４ ａ X ３－ａ (6) In formula (6), R ４ X and a are the same as those defined in formula (4) above.

[0107] Specific examples of reactive silicon group-containing hydrosilane compounds (F) include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, 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, (3,3,3-trifluoro Propyl)dimethoxysilane, (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-triph Examples include alkoxysilanes such as [dimethoxysilyloxy]dimethylsilane (diolopropyl); 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.

[0108] The amount of reactive silicon group-containing hydrosilane compound (F) used can be appropriately determined considering the amount of carbon-carbon unsaturated bonds in polymer (A) and the desired number of reactive silicon groups to be introduced.

[0109] Hydrosilylation reactions are preferably carried out in the presence of a hydrosilylation catalyst to accelerate the reaction. Known hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as complexes thereof, and these can be used. Specifically, these include platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid and alcohols, aldehydes, or ketones; and platinum-olefin complexes [e.g., Pt(CH4)]. ２ =CH ２ ) ２ (PPh ３ ), Pt(CH ２ =CH ２ ) ２ Cl ２ ]; Platinum-vinylsiloxane complex [e.g., Pt{(vinyl)Me ２ SiOSiMe ２ (vinyl)}, Pt{Me(vinyl)SiO} ４ ]; Platinum-phosphine complex [e.g., Ph(PPh ３ ) ４ , Pt(PBu ３ ) ４ ]; Platinum-phosphite complex [e.g., Pt{P(OPh) ３} ４ Examples include the following. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferred.

[0110] The amount of hydrosilylation catalyst used can be determined by conventional methods and is not particularly limited, but is approximately 10 per mole of carbon-carbon unsaturated bonds in polymer (A). －８ ~10 －１ It is preferable that the amount be in the mole range.

[0111] The hydrosilylation reaction can also be carried out in the presence of a quinone compound in addition to the hydrosilylation catalyst. The quinone compound can further enhance the acceleration of the hydrosilylation reaction by the hydrosilylation catalyst. Specific examples of quinone compounds include 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2-(1,2-dimethylpropyl)-9,10-anthraquinone. From the viewpoint of reaction efficiency, 2,5-di-tert-butyl-1,4-benzoquinone and 2,6-di-tert-butyl-1,4-benzoquinone are preferred. Further details regarding the use of the quinone compound can be found in Japanese Patent Application Publication No. 2000-94105.

[0112] Although the hydrosilylation reaction can be carried out without a solvent, an organic solvent may be added to ensure uniform dissolution of the polymer (A), the hydrosilane compound (F), and the hydrosilylation catalyst, and to facilitate temperature control of the reaction system and the addition of the hydrosilylation catalyst.

[0113] The temperature conditions for the hydrosilylation reaction are not particularly limited and can be set appropriately by those skilled in the art. However, to lower the viscosity of the reaction system and improve reactivity, the reaction is preferably carried out under heating conditions. Specifically, a reaction at 50°C to 150°C is more preferable, and a reaction at 70°C to 120°C is even more preferable. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions to prevent unintended condensation reactions between polymers. Specifically, the reaction time is preferably 30 minutes to 5 hours, and more preferably 3 hours or less.

[0114] Furthermore, the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This suppresses the thickening during the hydrosilylation reaction and improves the storage stability of the resulting polymer.

[0115] Examples of orthocarboxylic acid trialkyl esters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Trimethyl orthoformate and trimethyl orthoacetate are preferred.

[0116] When using orthocarboxylic acid trialkyl esters, the amount used is not particularly limited, but it is preferably about 0.1 to 10 parts by weight, and more preferably about 0.1 to 3 parts by weight, per 100 parts by weight of polymer (A).

[0117] By carrying out the hydrosilylation reaction described above, a polyoxyalkylene polymer (G) having pre-reactive silicon groups can be obtained with fewer steps compared to conventional methods. Polymer (G) has less bias in the reactive silicon and contains reactive silicon relatively uniformly.

[0118] <Curable Composition> A reactive silicon group-containing polyoxyalkylene polymer (G) can constitute a major component of a curable composition that can be cured in the presence of moisture. The curable composition preferably contains a silanol condensation catalyst for the purpose of promoting the reaction that hydrolyzes and condenses the reactive silicon groups, i.e., the curing reaction.

[0119] Conventional silanol condensation catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc.

[0120] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethylmaleate), dioctyltin bis(octylmaleate), dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds. Due to the growing environmental concerns in recent years, dioctyltin compounds are preferred.

[0121] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and cesium carboxylate. Various metals can be combined with the following carboxylic acids as carboxylate groups.

[0122] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0123] 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.

[0124] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxy titanium bis (ethylacetoacetate), aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0125] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0126] The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, using the aforementioned amine compound with a carboxylic acid, or with an amine compound with an alkoxy metal, may improve reactivity.

[0127] The amount of silanol condensation catalyst to be added is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of polymer (G), from the viewpoint of achieving both improved condensation reaction rate and workability during curing. Furthermore, some silanol condensation catalysts may seep out onto the surface of the cured product or contaminate the surface of the cured product after the curable composition has cured. In such cases, by using 0.01 to 3.0 parts by weight of silanol condensation catalyst, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0128] (Other Additives) The curable composition containing the reactive silicon group-containing polyoxyalkylene polymer (G) may also contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents.

[0129] 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 modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0130] <<Preparation of Curable Composition>> The curable composition can be prepared as a one-component type in which all components are pre-mixed and sealed for storage, and cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which components such as a silanol condensation catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and the mixture and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.

[0131] When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reducing pressure. Furthermore, storage stability can be further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane in addition to the dehydration and drying method.

[0132] The amount of dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is preferably in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (G).

[0133] <Applications> The curable composition can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., a waterproofing material, a waterproof coating material, a molding material, a vibration damping material, a soundproofing material, a foaming material, a paint, and a spray material. The cured product obtained by curing the curable composition according to this embodiment has excellent flexibility and adhesion, and can therefore be suitably used as a sealing material or an adhesive.

[0134] The following items list preferred embodiments of the present disclosure, but the present invention is not limited to these items. [Item 1] A method for producing a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds, comprising the steps of adding an epoxy compound (D) having carbon-carbon unsaturated bonds and not having an alicyclic structure, to a system containing a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide complex catalyst (C), without alkoxyling the hydroxyl groups of the polymer (B), and reacting the hydroxyl groups of the polymer (B) with the epoxy groups of the compound (D) at 115 to 160°C. [Item 2] The method for producing the present invention according to Item 1, wherein the addition of the epoxy compound (D) is carried out over time. [Item 3] The method for producing the present invention according to Item 2, wherein the time required to add an amount of epoxy compound (D) equal to the number of moles of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene polymer (B) is 3 to 30 minutes. [Item 4] A manufacturing method according to any one of Items 1 to 3, wherein the molar ratio expressed as the number of moles of epoxy compound (D) / the number of moles of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene polymer (B) is 1.5 to 50. [Item 5] A manufacturing method according to any one of Items 1 to 4, further comprising the step of polymerizing an alkylene oxide compound (E) in the presence of a complex metal cyanide catalyst (C) to form a hydroxyl group-containing polyoxyalkylene polymer (B), wherein the polymerization of the alkylene oxide compound (E) and the reaction between the polymer (B) and the epoxy compound (D) are carried out in succession. [Item 6] A manufacturing method according to any one of Items 1 to 5, wherein the epoxy compound (D) is allyl glycidyl ether. [Item 7] A manufacturing method according to any one of Items 1 to 6, wherein when adding the epoxy compound (D), no epoxy compound without a carbon-carbon unsaturated bond is added. [Item 8] A method for producing a product according to any one of Items 1 to 7, wherein the pH of the system comprising a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide catalyst (C) is 9 or less.[Item 9] A method for producing a reactive silicon group-containing polyoxyalkylene polymer (G), comprising the steps of: obtaining a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds by a manufacturing method described in any of Items 1 to 8; and hydrosilylation reacting the polymer (A) with a reactive silicon group-containing hydrosilane compound (F).

[0135] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0136] (Number-average molecular weight) The number-average molecular weight (Mn) of the polymer is the GPC molecular weight measured under the following conditions: Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSK-GEL H-type solvent: THF (tetrahydrofuran) Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

[0137] (Hydroxyl Value) The hydroxyl value (mol / g) of the hydroxyl group-containing initiator and the hydroxyl group-containing polyoxyalkylene polymer (B) was determined by the measurement method of JIS K 1557-1.

[0138] (pH) The pH of the hydroxyl group-containing polyoxyalkylene polymer (B) and the polymer obtained by alkoxyling polymer (B) were determined by the measurement method described in JIS Z 8802 (Method for measuring pH).

[0139] (Presence or absence of low molecular weight components in polymer (A)) The presence or absence of low molecular weight components in polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds was determined by measuring GPC under the above conditions and overlaying the GPC chart of polymer (B) before double bond addition with the GPC chart of polymer (A) after double bond addition, and checking whether a broad peak was observed in the elution time range of 12.5 to 15 minutes. This peak was interpreted as a low molecular weight component derived from epoxy compound (D) that did not contribute to the introduction of the double bond.

[0140] (Epoxy group consumption rate and introduction rate) The epoxy group consumption rate of epoxy compound (D) and the introduction rate into the polymer [the ratio of the ends to which epoxy compound (D) is introduced relative to the total ends of the polymer] in the reaction between polymer (B) and epoxy compound (D) are as follows for the manufactured polymer. １ The results were determined based on 1H NMR measurements. The epoxy group consumption rate of epoxy compound (D) was calculated from the rate of decrease in the integrated signal value originating from the epoxy groups of epoxy compound (D). The introduction rate was calculated from the ratio of the integrated signal values ​​originating from polymers in which epoxy compound (D) was introduced to polymers in which epoxy compound (D) was not introduced. A higher introduction rate indicates that carbon-carbon unsaturated bonds were introduced more uniformly into the manufactured polymer.

[0141] The above １ H-NMR measurements are performed using the following nuclear magnetic resonance (NMR) spectrometer, CDCl ３ The experiment was performed in a solvent. Equipment: AVANCE III HD500 digital instrument (manufactured by BRUKER).

[0142] (Synthesis Example 1) 0.27 g of a zinc hexacyanocobaltate glyme complex catalyst was used as the composite metal cyanide complex catalyst (C), 45 g of tetrahydrofuran (THF) was used as the solvent, 406 g of polyoxypropylene glycol (hydroxyl value 0.668 mmol / g) having two hydroxyl groups per molecule as a hydroxyl group-containing initiator was used as the hydroxyl group-containing initiator, and 45 g of propylene oxide (PO) was used as the alkylene oxide (E) was charged into a reaction vessel. The mixture was heated to 95°C while stirring with a stirrer to activate the catalyst. Next, while maintaining the internal temperature of the reaction vessel at 135°C, 449 g of propylene oxide was added over 90 minutes. After the addition, the polymerization reaction was continued for another 30 minutes to obtain 889 g of a hydroxyl group-containing polyoxyalkylene polymer (B1). The number-average molecular weight, hydroxyl value, and pH of the obtained polymer (B1) were measured according to the above description, and the results are shown in Table 1.

[0143] (Synthesis Examples 2-5) Hydroxyl group-containing polyoxyalkylene polymers (B2) to (B5) were obtained in the same manner as in Example 1, except that the conditions described in Table 1 were changed. In Synthesis Example 5, polyoxypropylene glycol (hydroxyl value 0.185 mmol / g) having two hydroxyl groups in one molecule was used as the hydroxyl group-containing initiator. The number average molecular weight, hydroxyl value, and pH of the obtained polymers (B2) to (B5) were measured in the same manner as in Synthesis Example 1, and the results are shown in Table 1. For polymer (B4), the pH was measured after removing THF from the obtained polymer.

[0144] (Reference Example 1) After obtaining a hydroxyl group-containing polyoxyalkylene polymer (B2), THF was removed, and the mixture containing polymer (B2) and zinc hexacyanocobaltate glyme complex catalyst was taken out of the reaction vessel. Then, 100 g of the mixture was charged into the reaction vessel, and 3.40 g of sodium methoxide as a 28% methanol solution was added. The polymer (B2) was alkoxylated by vacuum defloration at 140°C and methanol was removed by distillation. Then, the pH was measured in the same manner as in Synthesis Example 1. As a result, the pH of the alkoxylated polymer (B2) was 14.2.

[0145]

[0146] (Example 1) After obtaining the hydroxyl group-containing polyoxyalkylene polymer (B1) in Synthesis Example 1, the following treatment was carried out. In a reaction vessel containing 889 g of polymer (B1) obtained in Synthesis Example 1, a zinc hexacyanocobaltate glyme complex catalyst, and THF, 183 g of allyl glycidyl ether (AGE) as epoxy compound (D) was added over 24 minutes while maintaining the internal temperature of the reaction vessel at 135°C. After the addition was completed, the reaction was continued at the same temperature for 30 minutes, and then the THF was removed to obtain 1072 g of polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds at the terminals. For the obtained polymer (A), the epoxy group consumption rate and introduction rate of epoxy compound (D) were measured according to the above description, and the results are shown in Table 2. In addition, the presence or absence of low molecular weight components in polymer (A) was determined by GPC peaks, and the results are also shown in Table 2.

[0147] (Examples 2-9, 11, 12, Comparative Example 1) Polyoxyalkylene polymers (A) having carbon-carbon unsaturated bonds at the terminals were obtained in the same manner as in Example 1, except that the conditions described in Table 1 were changed. For each polymer (A) obtained, the epoxy group consumption rate and introduction rate of epoxy compound (D) were measured in the same manner as in Example 1, and the results are shown in Table 2. In addition, the presence or absence of low molecular weight components in polymer (A) was determined by GPC peaks, and the results are also shown in Table 2.

[0148] (Example 10) After obtaining a hydroxyl group-containing polyoxyalkylene polymer (B4), THF was removed, and the mixture containing polymer (B4) and zinc hexacyanocobaltate glyme complex catalyst was taken out of the reaction vessel. Then, 20 g of the mixture was charged into the reaction vessel, and while maintaining the internal temperature of the reaction vessel at 130°C, 1.14 g of allyl glycidyl ether (AGE) was added all at once as epoxy compound (D). After the addition was completed, the reaction was continued for 60 minutes to obtain 21 g of polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds at the terminals. The epoxy group consumption rate and introduction rate of epoxy compound (D) of the obtained polymer (A) were measured in the same manner as in Example 1, and the results are shown in Table 2. In addition, the presence or absence of low molecular weight components in polymer (A) was determined by GPC peaks, and the results are also shown in Table 2.

[0149] (Comparative Example 2) After obtaining a hydroxyl group-containing polyoxyalkylene polymer (B4), THF was removed, and the mixture containing polymer (B4) and zinc hexacyanocobaltate glyme complex catalyst was taken out of the reaction vessel. Then, 20 g of the mixture was charged into the reaction vessel, and while maintaining the internal temperature of the reaction vessel at 102°C, 1.14 g of allyl glycidyl ether (AGE) was added over 8 minutes as epoxy compound (D). After the addition was completed, the reaction was continued for 60 minutes to obtain 21 g of polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds at the terminals. The epoxy group consumption rate and introduction rate of epoxy compound (D) of the obtained polymer (A) were measured in the same manner as in Example 1, and the results are shown in Table 2. In addition, the presence or absence of low molecular weight components in polymer (A) was determined by GPC peaks, and the results are also shown in Table 2. In Table 2, "T hours (minutes)" refers to "the time required to add an amount of epoxy compound (D) equal to the number of moles of hydroxyl groups present in polymer (B)."

[0150]

[0151] The following can be seen from Table 2. In Comparative Examples 1 and 2, a hydroxyl group-containing polyoxyalkylene polymer (B) and an epoxy compound (D) were reacted at 110°C or 102°C in the presence of a complex metal cyanide catalyst (C). However, despite the complete consumption of the epoxy groups, the introduction rate, i.e., the proportion of polymer ends into which the epoxy compound (D) was introduced, was low.

[0152] In contrast to these comparative examples, Examples 1 to 12, in which a hydroxyl group-containing polyoxyalkylene polymer (B) and an epoxy compound (D) were reacted at a temperature of 115°C or higher in the presence of a complex metal cyanide catalyst (C), showed an improved introduction rate, indicating that the epoxy compound (D) was introduced relatively uniformly to the polymer ends. Furthermore, in Examples 1 to 9 and 11 to 12, in which the epoxy compound (D) was added over time, it was found that the generation of low molecular weight components was suppressed.

[0153] (Synthesis Example 6) 100 parts by weight of polymer (A) obtained by the procedure of Example 4 was mixed with 200 parts by weight of n-hexane and stirred. Further, 30 parts by weight of synthetic aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700 SEN-S) and 10 parts by weight of Standard Supercell (Nacalai Tesque Co., Ltd.) were added and stirred, and the mixture was stopped after 60 minutes. The synthetic aluminum silicate was removed by vacuum suction filtration using a Kiriyama funnel lined with filter paper, Celite-545RVS (Nacalai Tesque Co., Ltd.), and the aforementioned Standard Supercell. After washing the residue on the Kiriyama funnel with n-hexane, the filtrate was concentrated in an evaporator to remove n-hexane, thereby removing the complex metal cyanide catalyst (C) from polymer (A). To 500 g of polymer (A), 43 μl of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 11.8 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting at 90°C for 0.5 hours, the unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a reactive silicon-containing polyoxyalkylene polymer (G).

[0154] As shown in the synthesis examples above, a reactive silicon-containing polyoxyalkylene polymer (G) could be synthesized by hydrosilylation reaction between polymer (A) and a reactive silicon-containing hydrosilane compound (F).

Claims

1. A method for producing a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds, comprising the steps of adding an epoxy compound (D) having carbon-carbon unsaturated bonds and not having an alicyclic structure, to a system containing a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide complex catalyst (C), without alkoxyling the hydroxyl groups of polymer (B), and reacting the hydroxyl groups of polymer (B) with the epoxy groups of compound (D) at 115 to 160°C.

2. The manufacturing method according to claim 1, wherein the epoxy compound (D) is added over time.

3. The manufacturing method according to claim 2, wherein the time required to add an epoxy compound (D) in an amount equal to the number of moles of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene polymer (B) is 3 to 30 minutes.

4. The manufacturing method according to any one of claims 1 to 3, wherein the molar ratio expressed as the number of moles of epoxy compound (D) / the number of moles of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene polymer (B) is 1.5 to 50.

5. The manufacturing method according to any one of claims 1 to 3, further comprising the step of polymerizing an alkylene oxide compound (E) in the presence of a complex metal cyanide catalyst (C) to form a hydroxyl group-containing polyoxyalkylene polymer (B), wherein the polymerization of the alkylene oxide compound (E) and the reaction between the polymer (B) and the epoxy compound (D) are carried out in succession.

6. The manufacturing method according to any one of claims 1 to 3, wherein the epoxy compound (D) is allyl glycidyl ether.

7. The manufacturing method according to any one of claims 1 to 3, wherein when epoxy compound (D) is added, an epoxy compound that does not have a carbon-carbon unsaturated bond is not added.

8. The method for producing a product according to any one of claims 1 to 3, wherein the pH of the system comprising a hydroxyl group-containing polyoxyalkylene polymer (B) and a complex metal cyanide catalyst (C) is 9 or less.

9. A method for producing a reactive silicon group-containing polyoxyalkylene polymer (G), comprising the steps of: obtaining a polyoxyalkylene polymer (A) having carbon-carbon unsaturated bonds by a manufacturing method described in any one of claims 1 to 3; and hydrosilylation reacting the polymer (A) with a reactive silicon group-containing hydrosilane compound (F).

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