Method for producing polyether polyol, method for producing polyether polyol having reactive silicon group, and polyether polyol

Abstract

This method for producing a polyether polyol produces a polyether polyol by reacting a cyclic ether with an initiator which has a melting point of 150°C or less, while comprising 8 or more functional groups in the presence of a catalyst.

Description

Method for producing polyether polyol, method for producing polyether polyol having reactive silicon group, and polyether polyol

[0001] The present invention relates to a method for producing a polyether polyol, a method for producing a polyether polyol having reactive silicon groups, and a polyether polyol, and in particular to a method for producing a polyether polyol having reactive silicon groups, in which a polyether polyol obtained by the production method is used to produce a polyether polyol having reactive silicon groups, and a polyether polyol.

[0002] Polyether polyols are known to be used as polyurethane resin raw materials and nonionic surfactants, and are also used as raw materials for curable materials by modifying the terminal hydroxyl groups. Polyether polyols having reactive silicon groups are known to crosslink even at room temperature through the formation of siloxane bonds accompanied by hydrolysis of the reactive silicon groups due to moisture or the like, to produce rubber-like cured products. They are already industrially produced and widely used in applications such as sealants, adhesives, and paints (see, for example, Patent Documents 1 to 3).

[0003] Japanese Patent Publication No. 2020-176169 Japanese Patent Publication No. 2009-46539 Chinese Patent Application Publication No. 110922579

[0004] However, polyether polyols useful as raw materials for polyether polyols having reactive silicon groups generally have the problem that when the molecular weight of a conventional initiator having 2 to 6 functional groups is extended to a certain level, the viscosity increases rapidly, making the mixture impossible to stir, and making synthesis difficult.

[0005] The present invention has been made in view of the above circumstances, and provides a method for producing a polyether polyol that can easily provide a polyether polyol that serves as a raw material for a polyether polyol having reactive silicon groups, which has improved surface curing rate and shear strength expression while maintaining the flexibility and elasticity of the cured product; a method for producing a polyether polyol having reactive silicon groups using the polyether polyol obtained by the production method; and a polyether polyol.

[0006] The present invention has the following aspects. [1] A method for producing a polyether polyol, comprising reacting an initiator having 8 or more functional groups and a melting point of 150°C or less with a cyclic ether in the presence of a catalyst to produce a polyether polyol. [2] A method for producing a polyether polyol as described in [1] above, wherein the polyether polyol has a hydroxyl value-based molecular weight of 20,000 or more and 500,000 or less. [3] A method for producing a polyether polyol as described in [1] or [2] above, wherein the initiator has a highly branched structure. [4] A method for producing a polyether polyol as described in any of [1] to [3] above, wherein the proportion of primary hydroxyl groups in the hydroxyl groups of the entire initiator is 50 to 95%. [5] A method for producing a polyether polyol as described in any of [1] to [4] above, wherein the polyether polyol has a total degree of unsaturation of 0.01 meq / g or less. [6] A method for producing a polyether polyol as described in any of [1] to [5] above, wherein the catalyst is a double metal cyanide complex catalyst. [7] A method for producing a polyether polyol according to any one of [1] to [6] above, wherein the cyclic ether is fed over an addition time of 4 to 60 hours to react with the initiator. [8] A method for producing a polyether polyol according to any one of [1] to [7] above, wherein the cyclic ether is at least one of ethylene oxide and propylene oxide. [9] A method for producing a polyether polyol according to any one of [1] to [8] above, wherein the viscosity of the polyether polyol at 25°C is 100,000 mPa s or less.

[10] A method for producing a polyether polyol having a reactive silicon group, comprising using a polyether polyol obtained by the method for producing a polyether polyol according to any one of [1] to [9] above, wherein hydroxyl groups in the polyether polyol are converted to groups having a reactive silicon group represented by the following formula (1) by the following (Method 1) or (Method 2):(Method 1) A method of converting hydroxyl groups in the polyether polyol to groups containing unsaturated groups to obtain polyether polyol (a), and then reacting the unsaturated groups in the polyether polyol (a) with a silylating agent (A) having a group reactive with the unsaturated group and a reactive silicon group represented by the following formula (1): (Method 2) A method of reacting hydroxyl groups in the polyether polyol with a silylating agent (B) having a group reactive with the hydroxyl group and a reactive silicon group represented by the following formula (1): —SiR. ａ (X) ３－ａ (1) (In formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.

[11] The method for producing a polyether polyol having a reactive silicon group according to the above

[10] , wherein the silylation rate of the polyether polyol having a reactive silicon group is 60% or more.

[12] The method for producing a polyether polyol having a reactive silicon group according to the above

[10] or

[11] , wherein the polyether polyol having a reactive silicon group has a urethane bond.

[13] A polyether polyol having a highly branched structure, a polyoxyalkylene chain, and eight or more hydroxyl group molecular chain terminals, wherein the hydroxyl value-based molecular weight of the polyether polyol is 20,000 to 500,000.

[0007] According to the present invention, it is possible to provide a method for producing a polyether polyol that can easily obtain a polyether polyol that serves as a raw material for a polyether polyol having reactive silicon groups, which has improved surface curing rate and shear strength expression while maintaining the flexibility and elasticity of the cured product; a method for producing a polyether polyol having reactive silicon groups using the polyether polyol obtained by the production method; and a polyether polyol.

[0008] The meanings and definitions of terms used in this specification are as follows. A numerical range expressed as "to" means a numerical range with the numerical values ​​before and after "to" as the lower and upper limits. An "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group formed by removing one hydrogen atom from a primary amine, and a sulfanyl group. An "active hydrogen" is a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from a hydroxyl group of water. An "initiator" is a compound having an active hydrogen-containing group. An "unsaturated group" means a monovalent group containing an unsaturated double bond. Unless otherwise specified, it is at least one group selected from the group consisting of a vinyl group, an allyl group, and an isopropenyl group.

[0009] The term "oxyalkylene polymer" refers to a polymer having a polyoxyalkylene chain formed from units based on a cyclic ether. In a polyoxyalkylene polymer having a main chain containing a polyoxyalkylene chain and a terminal group bonded to the main chain, the "terminal group" refers to an atomic group containing the oxygen atom in the polyoxyalkylene chain that is closest to the molecular terminal of the oxyalkylene polymer.

[0010] The term "precursor polymer" refers to an oxyalkylene polymer before the introduction of reactive silicon groups, in which the terminal groups formed by polymerizing a cyclic ether to the active hydrogen of the initiator are hydroxyl groups. The term "silylation rate" refers to the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups of the oxyalkylene polymer. The value of the silylation rate can be measured by NMR analysis. Alternatively, the term "silylation rate" may refer to the ratio (mol %) of the number of silyl groups of the silylating agent added to the precursor polymer derivative when the reactive silicon groups are introduced to the terminal groups of the precursor polymer derivative using a silylating agent to the total number of active hydrogen-containing groups and unsaturated groups of the precursor polymer derivative. The term "silylating agent" refers to a compound having a functional group reactive with an active hydrogen-containing group or an unsaturated group and a reactive silicon group. The term "the initiator has a highly branched structure" refers to an initiator having 8 or more functional groups, a branched structure, and in which 50% or more of the hydroxyl groups in the entire initiator are primary hydroxyl groups.

[0011] The "hydroxyl value-equivalent molecular weight (OHV value-equivalent molecular weight)" is a value calculated by calculating the hydroxyl value of an initiator or a precursor polymer based on JIS K 1557 (2007) as "56,100 / (hydroxyl value) × (the number of active hydrogen atoms in the initiator, or the number of terminal groups in the precursor polymer)."

[0012] The number average molecular weight (hereinafter referred to as "Mn") and weight average molecular weight (hereinafter referred to as "Mw") of the polymer are polystyrene-equivalent molecular weights obtained by GPC measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is the ratio of Mw to Mn (hereinafter referred to as "Mw / Mn").

[0013] [Method for Producing Polyether Polyol] The method for producing a polyether polyol of the present invention is a method for producing a polyether polyol by reacting an initiator having 8 or more functional groups and a melting point of 150° C. or less with a cyclic ether in the presence of a catalyst. In the present specification, the phrase "reacting an initiator with a cyclic ether" does not only mean "directly reacting an initiator (e.g., polyglycerol in Synthesis Example 1 described later) with a cyclic ether (e.g., propylene oxide in Synthesis Example 1 described later)," but also refers to a concept that includes "directly reacting a cyclic ether with an initiator" and "reacting a product produced by the reaction of an initiator with a cyclic ether (e.g., polyol (b) in Synthesis Example 1 described later) with a cyclic ether."

[0014] <Initiator> The initiator is not particularly limited as long as it has eight or more functional groups and a melting point of 150°C or less, and examples thereof include polyglycerin, tripentaerythritol, polyvinyl alcohol, and polyglycerol. Among these, initiators having a highly branched structure are preferred. For example, polyglycerols having a highly branched structure include branched polyglycerols having eight or more functional groups and being more branched than linear polyglycerols (see structural formula (a) below). As the branched polyglycerol, at least one selected from the group consisting of hyperbranched polyglycerols (see structural formula (b) below), glycerol dendrons (see structural formula (c) below), and polyglycerol dendrimers (see structural formula (d) below) is preferred, with polyglycerol dendrimers being more preferred. Herein, the "proportion (abundance ratio) of primary hydroxyl groups among the hydroxyl groups in the entire initiator" (hereinafter also referred to as the "primary content ratio") is measured by the following method. The primary content was measured by the method described in the patent document (JP-A-2000-344881), in which a sample was esterified with trifluoroacetic anhydride, and then: １ The peak area derived from primary hydroxyl groups and the peak area derived from secondary hydroxyl groups can be obtained by H-NMR and calculated using the following formula (X): Primary content (%) = [a / (a+2×b)]× 100 Formula (X) where a is the peak area derived from primary hydroxyl groups around 4.3 ppm, and b is the peak area derived from secondary hydroxyl groups around 5.2 ppm. The "proportion (abundance ratio) of primary hydroxyl groups among the total hydroxyl groups in the initiator" is not particularly limited, but is preferably 50% or more, more preferably 50 to 95%, and even more preferably 55 to 90%, in terms of ease of terminal modification. Note that using sugars that are solid at room temperature as initiators is undesirable in that the reaction solution containing the initiator becomes highly viscous, making polymerization impossible without the use of a solvent or diluent (water, glycerin).

[0015]

[0016] ​Specific examples of commercially available initiators include (1) polyglycerin (hyperbranched polymer (see the following structural formula)) manufactured by Daicel Corporation ((i) PGL10PSW (number of functional groups: 12, degree of polymerization: 10, melting point: 12°C, proportion (abundance ratio) of primary hydroxyl groups in the entire hydroxyl groups of the initiator): 60%), (ii) PGL20PW (number of functional groups: 22, degree of polymerization: 20, melting point: 17°C, proportion (abundance ratio) of primary hydroxyl groups in the entire hydroxyl groups of the initiator): 65%), (iii) PGL X (number of functional groups: 42, degree of polymerization: 40, melting point: 9°C, proportion (abundance ratio) of primary hydroxyl groups in the entire hydroxyl groups of the initiator): 62%)), (2) polyglycerin (linear, number of functional groups: 12, proportion (abundance ratio) of primary hydroxyl groups in the entire hydroxyl groups of the initiator): 17%) manufactured by Sakamoto Pharmaceutical Industry Co., Ltd. Dendrimer (QUICK STAR) manufactured by TECH (Instrumental Polymer Technologies) Inc., and the like.

[0017] The number of functional groups of the initiator refers to the number of hydroxyl groups per molecule of the initiator. The number of functional groups of the initiator is not particularly limited as long as it is 8 or more, but is preferably 8 to 60, more preferably 9 to 50, and even more preferably 10 to 45. When a polyether polyol having a reactive silicon group is obtained by making the number of functional groups of the initiator 8 or more, the curing rate of the polyether polyol having the reactive silicon group can be improved, and by making the number of functional groups of the initiator within a preferred range, the curing rate of the polyether polyol having the reactive silicon group can be further improved.

[0018] The melting point of the initiator is not particularly limited as long as it is 150°C or less, but is preferably -50 to 100°C, more preferably -50 to 90°C, even more preferably -20 to 70°C, and particularly preferably 5 to 60°C. By setting the melting point of the initiator to 150°C or less, the initiator becomes easier to handle, thereby improving reactivity. Furthermore, by setting the melting point of the initiator within a preferred range, the resulting polyether polyol tends to be easier to handle. Note that the "melting point of the initiator" here is measured by the same method as in the examples described below.

[0019] <Cyclic Ethers> Examples of cyclic ethers include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide; and cyclic ethers other than alkylene oxides such as tetrahydrofuran. These may be used alone or in combination of two or more. Among these, at least one of ethylene oxide (hereinafter referred to as "EO") and propylene oxide (hereinafter referred to as "PO") is preferred, with PO being more preferred, in terms of good reactivity.

[0020] The addition time (feed time) when feeding the cyclic ether to react with the initiator is not particularly limited, but is preferably 4 to 60 hours, more preferably 6 to 50 hours, and even more preferably 10 to 40 hours in terms of making production more efficient. Note that the addition time (feed time) does not vary depending on the reaction scale, and is therefore different from the feed rate, which varies depending on the reaction scale.

[0021] The amount of cyclic ether added per 100 parts by mass of initiator is not particularly limited, but is preferably 1,000 to 10,000 parts by mass, more preferably 2,000 to 9,000 parts by mass, and even more preferably 2,500 to 8,000 parts by mass, in that when a polyether polyol having a reactive silicon group is obtained, the tensile properties of the cured product of the polyether polyol having a reactive silicon group tend to be good.

[0022] <Catalyst> Conventional catalysts can be used as the catalyst, including, for example, alkaline catalysts such as KOH, transition metal compound-porphyrin complex catalysts such as complexes obtained by reacting an organoaluminum compound with porphyrin, composite metal cyanide complex catalysts, and catalysts composed of phosphazene compounds. These catalysts can be used alone or in combination of two or more. Among these, composite metal cyanide complex catalysts are preferred because they facilitate the production of polyether polyols (precursor polymers) with low degrees of unsaturation. Conventional compounds can be used as composite metal cyanide complex catalysts, and known methods can be used to produce polymers using composite metal cyanide complexes. For example, compounds and production methods disclosed in WO 2003 / 062301, WO 2004 / 067633, JP 2004-269776 A, JP 2005-15786 A, WO 2013 / 065802 A, and JP 2015-010162 A can be used.

[0023] The amount of catalyst added relative to 100 parts by mass of the initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, in terms of making the reaction proceed quickly.

[0024] [Polyether polyol (precursor polymer)] The polyether polyol (precursor polymer) of the present invention is a polyether polyol having a highly branched structure, a polyoxyalkylene chain, eight or more hydroxyl group terminals, and a hydroxyl value-based molecular weight of 20,000 to 500,000. The polyether polyol (precursor polymer) may be one produced by the polyether polyol production method of the present invention, or may not be one produced by the polyether polyol production method of the present invention.

[0025] <Highly branched structure> The highly branched structure of a polyether polyol (precursor polymer) is a structure derived from an initiator having a highly branched structure. It is a structure formed by extending a polyoxyalkylene chain derived from a cyclic ether from a hydroxyl group portion of an initiator having a highly branched structure. A polyether polyol (precursor polymer) having such a highly branched structure is sometimes called a "dendrimer" or a "hyperbranched polymer." A "dendrimer" or a "hyperbranched polymer" has a structure in which a molecular chain extending from a branch point present at a central point further has branch points, and the number of terminals increases with increasing distance from the central point.

[0026] "Dendrimers" are highly branched polymers and oligomers that may be in the form of assemblies of molecules of the same generation, so-called monodisperse assemblies, or of different generations, so-called polydisperse assemblies. The definition of "dendrimer" includes dense star polymers, starburst polymers, rod-shaped dendrimers, arborols, cascade molecules, bridged dendrimers, dendrimer assemblies, and the like.

[0027] A "hyperbranched polymer" is generally a molecular structure having branches around a core. The structure generally lacks symmetry, and the monomers or base units used to construct the "hyperbranched polymer" are of various types and are not distributed uniformly. The branches of the polymer can be of various types and lengths. The number of base units or monomers can vary depending on the different branches. The definition of "hyperbranched polymer" also includes bridged polymers.

[0028] <Polyoxyalkylene Chain> Examples of polyoxyalkylene chains include polyoxypropylene chains, polyoxyethylene chains, poly(oxy-2-ethylethylene) chains, poly(oxy-1,2-dimethylethylene) chains, poly(oxytetramethylene) chains, poly(oxyethylene-oxypropylene) chains, and poly(oxypropylene-oxy-2-ethylethylene) chains. The polyoxyalkylene chain may be a copolymer chain having two or more types of oxyalkylene groups. The copolymer chain may be a block copolymer chain or a random copolymer chain. Among these, polyoxypropylene chains and poly(oxyethylene-oxypropylene) chains are preferred, and polyoxypropylene chains are more preferred, in that when a polyether polyol having a reactive silicon group is obtained, the tensile properties and shear strength of the polyether polyol having the reactive silicon group are likely to be improved.

[0029] <Molecular Chain Ends> The polyether polyol (precursor polymer) has eight or more molecular chain ends that are hydroxyl groups. When a polyether polyol having a reactive silicon group is obtained, the number of molecular chain ends that are hydroxyl groups in the polyether polyol (precursor polymer) is preferably 8 to 60, more preferably 9 to 50, and even more preferably 10 to 45, in order to facilitate improvements in the tensile properties and shear strength of the polyether polyol having a reactive silicon group. When the polyether polyol (precursor polymer) has eight or more molecular chain ends that are hydroxyl groups, the tack-free time of the cured product is short and the deep curing properties are excellent. The terminal group of the polyoxyalkylene chain in the polyether polyol (precursor polymer) is a hydroxyl group. When the polyoxyalkylene chain is a polyoxypropylene chain derived from PO, the hydroxyl group at the terminal group of the polyoxyalkylene chain is a secondary hydroxyl group, and when it is a polyoxyethylene chain derived from EO, the hydroxyl group at the terminal group of the polyoxyalkylene chain is a primary hydroxyl group.

[0030] The hydroxyl value-based molecular weight of the polyether polyol (precursor polymer) is not particularly limited, but when a polyether polyol having a reactive silicon group is obtained, the tensile properties of the polyether polyol having the reactive silicon group are likely to be improved, so it is preferably 20,000 to 500,000, more preferably 20,000 to 300,000, even more preferably 25,000 to 250,000, and even more preferably 30,000 to 200,000. Note that the "hydroxyl value-based molecular weight of the polyether polyol (precursor polymer)" here is measured by the same method as in the examples described below.

[0031] The total unsaturation value (USV) of the polyether polyol (precursor polymer) is not particularly limited, but in terms of ease of terminal modification, it is preferably 0.01 meq / g or less, more preferably 0.001 to 0.009 meq / g, and even more preferably 0.003 to 0.008 meq / g. The "total unsaturation value (USV) of the polyether polyol (precursor polymer)" here is measured by the same method as in the examples described below.

[0032] The viscosity of the polyether polyol (precursor polymer) at 25°C is not particularly limited, but from the viewpoint of ease of handling, it is preferably 100,000 mPa·s or less, more preferably 1,000 to 80,000 mPa·s, and even more preferably 2,000 to 50,000 mPa·s. Note that the "viscosity of the polyether polyol (precursor polymer) at 25°C" here is measured by the same method as in the examples described below.

[0033] [Method for producing polyether polyol having reactive silicon groups] The method for producing a polyether polyol having reactive silicon groups of the present invention involves using a polyether polyol obtained by the method for producing a polyether polyol of the present invention to produce a polyether polyol having reactive silicon groups, and converting the hydroxyl groups in the polyether polyol to groups having reactive silicon groups represented by the following formula (1) by the following (Method 1) or (Method 2). The polyether polyol having reactive silicon groups produced by the method for producing a polyether polyol having reactive silicon groups of the present invention preferably has a urethane bond. (Method 1) A method in which the hydroxyl groups in the polyether polyol are converted to groups containing an unsaturated group to obtain polyether polyol (a), and the unsaturated group in the polyether polyol (a) is reacted with a silylating agent (A) having a group reactive with the unsaturated group and a reactive silicon group represented by the following formula (1): (Method 2) A method of reacting the hydroxyl groups of the polyether polyol with a silylating agent (B) having a group reactive with the hydroxyl group and a reactive silicon group represented by the following formula (1): —SiR ａ (X) ３－ａ (1) (In formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a represents an integer of 0 to 2. When a is 2, R may be the same or different from one another, and when a is 0 or 1, X may be the same or different from one another.)

[0034] In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain a hydrolyzable group. R is preferably at least one selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0035] R is preferably at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-chloroalkyl group, and a triorganosiloxy group. It is more preferably at least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group. From the viewpoint of good curability of the polyether polyol having a reactive silicon group and good stability of the curable composition, a methyl group or an ethyl group is even more preferred. An α-chloromethyl group is even more preferred from the viewpoint of a fast curing rate of the cured product. A methyl group is even more preferred from the viewpoint of easy availability.

[0036] In the formula (1), X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. X may be the same or different. Examples of the hydrolyzable group include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. Among these, an alkoxy group is preferred because of its mild hydrolysis and ease of handling. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed, making it easy to form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0037] In the formula (1), a is an integer of 0 to 2. When a is 2, R's may be the same or different from each other. When a is 0 or 1, X's may be the same or different from each other. A value of 0 is preferred because it provides good curability.

[0038] Examples of the reactive silicon group represented by formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, an (α-chloromethyl)diethoxysilyl group, etc. Among these, in terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, and a methyldiethoxysilyl group are preferred, and a methyldimethoxysilyl group and a trimethoxysilyl group are more preferred.

[0039] Since the polyether polyol having a reactive silicon group has the reactive silicon group represented by the formula (1), a curable composition containing the polyether polyol having a reactive silicon group has excellent curability.

[0040] The terminal group of the polyether polyol having a reactive silicon group may contain a group represented by the following formula (2) or (3): X in the following formula (3) １ is a monovalent group represented by any one of the following formulas (4) to (7): Si in the following formula (2) and the following formulas (4) to (7) １ represents a reactive silicon group represented by the formula (1). １ When present, they may be the same or different from one another.

[0041]

[0042] In formula (2), R １ , R ３ R each independently represents a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to the carbon atom in the linking group is a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom. １ , R ３ Examples of the group include -CH ２ -, -C ２ H ４ -, -C ３ H ６ -, -C４ H ８ -, -C ５ H １０ -, -C ６ H １２ -, -C(CH ３ ) ２ -, -CH ２ O-, -CH ２ -O-CH ２ -, -CH ２ -O-CH ２ -O-CH ２ -, -C=C-, -C≡C-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N-, -CH=N-N=CH-, and the like. １ Ha-CH ２ -O-CH ２ -, -CH ２ O-, -CH ２ - is preferred, and -CH ２ -O-CH ２ - is more preferable. ３ is -CH ２ -, -C ２ H ４ - is preferred, and -CH ２ - is more preferable.

[0043] R in formula (2) ２ , R ４are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred. Examples of linear alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of branched alkyl groups include an isopropyl group, an s-butyl group, a t-butyl group, a 2-methylbutyl group, a 2-ethylbutyl group, a 2-propylbutyl group, a 3-methylbutyl group, a 3-ethylbutyl group, a 3-propylbutyl group, a 2-methylpentyl group, a 2-ethylpentyl group, a 2-propylpentyl group, a 3-methylpentyl group, a 3-ethylpentyl group, a 3-propylpentyl group, a 4-methylpentyl group, a 4-ethylpentyl group, a 4-propylpentyl group, a 2-methylhexyl group, a 2-ethylhexyl group, a 2-propylhexyl group, a 3-methylhexyl group, a 3-ethylhexyl group, a 3-propylhexyl group, a 4-methylhexyl group, a 4-ethylhexyl group, a 4-propylhexyl group, a 5-methylhexyl group, a 5-ethylhexyl group, a 5-propylhexyl group, and the like. ２ , R ４ are each independently preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group.

[0044] In formula (2), n represents an integer of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.

[0045]

[0046] In formula (3), R ５ represents a single bond or a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to the carbon atom in the linking group is a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom. ５ Examples of the divalent linking group in １ , R ３ The examples of the divalent linking group are the same as those of the divalent linking group in R ５is preferably a single bond or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and even more preferably a single bond or a methylene group.

[0047] In formula (6), R ６ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. ６ Examples of the monovalent hydrocarbon group in R ２ , R ４ The examples of the monovalent hydrocarbon group are the same as those in R. ６ is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

[0048] R in formula (7) ７ , R ８ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms. The hydrocarbon group is preferably a linear or branched alkyl group having 1 to 9 carbon atoms. ７ , R ８ Examples of the alkyl group as R ２ , R ４ The alkyl groups are the same as those exemplified above. ７ , R ８ are preferably all hydrogen atoms.

[0049] <Silylating Agent (A)> Examples of the silylating agent (A) include compounds having both a group capable of reacting with an unsaturated group to form a bond (e.g., a sulfanyl group) and the reactive silicon group; hydrosilane compounds (e.g., HSiR ａ (X) ３－ａ, where X, R, and a are the same as in formula (1). Specific examples of the silylating agent (A) include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. Among these, trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferred, and methyldimethoxysilane or trimethoxysilane is more preferred, in that they have high activity and provide good curing properties.

[0050] The amount of the silylating agent (A) added is not particularly limited, but from the viewpoint of allowing the silylating agent to react more efficiently, it is preferably 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, and even more preferably 0.8 to 1.2 equivalents relative to the number of moles of unsaturated groups in the polyether polyol (a) having a group containing a converted unsaturated group.

[0051] <Silylating Agent (B)> As the silylating agent (B), a conventionally known isocyanate silane compound described in JP 2011-178955 A can be used, and examples thereof include 1-isocyanate methyl dimethoxymethyl silane, 1-isocyanate methyl diethoxyethyl silane, 3-isocyanate propyl methyl dimethoxysilane, 3-isocyanate propyl methyl diethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, isocyanate methyl methyl dimethoxysilane, isocyanate methyl methyl diethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, etc. Among these, 3-isocyanate propyl trimethoxysilane is preferred because of its better reactivity.

[0052] The molar ratio (NCO / OH molar ratio) of the isocyanate groups of the silylating agent (B) to the hydroxyl groups of the polyether polyol (precursor polymer) is not particularly limited, but is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, and even more preferably 0.8 to 1.2, in terms of ease of control of the degree of terminal modification.

[0053] As a method of introducing 1.0 or less unsaturated groups per terminal group of a precursor polymer and then reacting the unsaturated groups with a silylating agent (A), or a method of subjecting an active hydrogen-containing group in an terminal group of the precursor polymer to a urethane-forming reaction with a silylating agent (B), a conventionally known method can be used. Examples of the method include those proposed in JP-B Nos. 45-36319, 50-156599, 61-197631, 3-72527, 8-231707, 2011-178955, U.S. Pat. No. 3,632,557, and 4,960,844.

[0054] Furthermore, as a method for introducing an average of more than 1.0 unsaturated groups per terminal group of a polyether polyol (precursor polymer) and then reacting the unsaturated groups with the silylating agent (A), a conventionally known method can be used. For example, methods described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, JP 2015-105293, JP 2015-105322, JP 2015-105323, JP 2015-105324, WO 2015 / 080067, WO 2015 / 105122, WO 2015 / 111577, WO 2016 / 002907, JP 2016-216633, and JP 2017-39782 can be used.

[0055] As a method for introducing more than 1.0 unsaturated group per terminal group into the terminal groups of a polyether polyol (precursor polymer), a method in which an alkali metal salt is reacted with a polyether polyol (precursor polymer), followed by reaction with an epoxy compound having an unsaturated group, and then reaction with a halogenated hydrocarbon compound having an unsaturated group, or a method in which an alkali metal salt is reacted with a polyether polyol (precursor polymer), followed by reaction with a halogenated hydrocarbon compound having a carbon-carbon triple bond, is preferred.

[0056] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. Among these, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred from the viewpoints of ease of handling and solubility, sodium methoxide and potassium ethoxide are more preferred, and sodium methoxide is even more preferred from the viewpoint of availability. The alkali metal salt may be used in a state dissolved in a solvent.

[0057] Examples of epoxy compounds having an unsaturated group include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, 1,4-cyclopentadiene monoepoxide, etc. Among these, allyl glycidyl ether is preferred.

[0058] The epoxy compound having an unsaturated group is preferably a compound represented by the following formula (8):

[0059]

[0060] In formula (8), R １ , R ２ is R in the formula (2). １ , R ２ is the same as

[0061] As the halogenated hydrocarbon compound having an unsaturated group, one or both of a halogenated hydrocarbon compound containing a carbon-carbon double bond and a halogenated hydrocarbon compound containing a carbon-carbon triple bond can be used. Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Among these, allyl chloride and methallyl chloride are preferred. Examples of halogenated hydrocarbon compounds containing a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo Examples of halogenated hydrocarbon compounds having an unsaturated group include 1-iodo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Among these, propargyl chloride, propargyl bromide, and propargyl iodide are preferred. Two or more halogenated hydrocarbon compounds having an unsaturated group may be used in combination.

[0062] The reaction results in a derivative having more than 1.0 unsaturated group introduced per terminal group of the polyether polyol (precursor polymer). The polyether polyol (precursor polymer) derivative may contain unreacted active hydrogen-containing groups at the terminal groups. From the viewpoint of storage stability, the number of active hydrogen-containing groups contained in the polyether polyol (precursor polymer) derivative is preferably 0.3 or less, more preferably 0.1 or less per molecule.

[0063] The silylation rate of the polyether polyol having a reactive silicon group is not particularly limited, but is preferably 60% or more, more preferably 70% or more, and even more preferably 80 to 98%, in order to improve the curability of the polyether polyol having a reactive silicon group.

[0064] The silylation rate is calculated as follows: (Calculation of the silylation rate of polyether polyol having reactive silicon groups) In a method of introducing unsaturated groups into the terminal groups of a precursor polymer using allyl chloride and then reacting a silylating agent with the unsaturated groups to introduce reactive silicon groups, the silylation rate (mol %) is the equivalent of the reactive silicon groups of the silylating agent relative to the unsaturated groups introduced into the terminal groups. In the reaction of the silylating agent with the unsaturated groups introduced into the terminal groups of the precursor polymer using allyl chloride, the proportion of unsaturated groups that do not react with the silylating agent due to side reactions is approximately 15 mol %. Therefore, when less than 85 mol % of the unsaturated groups are reacted with the silylating agent, the equivalent of the isocyanate groups is equal to the silylation rate. In a method of subjecting the hydroxyl groups of a precursor polymer to a urethanization reaction with an isocyanate silane compound, the silylation rate (mol %) is the equivalent of the isocyanate groups of the isocyanate silane compound relative to the hydroxyl groups of the precursor polymer.

[0065] <Curable Composition> The curable composition is obtained by mixing a polyether polyol having a reactive silicon group with other necessary components. The proportion of the polyether polyol having a reactive silicon group relative to the total mass of the curable composition is not particularly limited, but is preferably 1 to 50 mass%, more preferably 2 to 45 mass%, and even more preferably 4 to 40 mass%. Within this preferred range, the cured product of the curable composition will have excellent elongation.

[0066] The curable composition may be a one-component type in which the reactive silicon group-containing polyether polyol and all other components are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application, or a two-component type in which a base composition containing at least the reactive silicon group-containing polyether polyol and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the base composition are mixed before use. One-component curable compositions are preferred because they are easier to apply.

[0067] It is preferable that the one-component curable composition does not contain water. It is preferable that the blending components containing water are dehydrated and dried in advance, or that the pressure is reduced during blending and kneading to dehydrate them. In the two-component curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable that the blending components are dehydrated and dried in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0068] (Other Components) Examples of the other components include polymers other than polyether polyols having reactive silicon groups, acrylic silicones, epoxy resins, epoxy resin curing agents, curable compounds, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropy-imparting agents, stabilizers, antioxidants, ultraviolet absorbers, dehydrating agents, adhesion-imparting agents, physical property adjusters, tackifying resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, silicates, and the like. Other components may be used in combination without limitation with conventionally known components described in International Publication Nos. 2013 / 180203, 2014 / 192842, 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0069] The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples, and various modifications are possible within the scope of the present invention. Of Synthesis Examples 1 to 13, Synthesis Examples 1 to 8 are Synthesis Examples, and Synthesis Examples 9 to 13 are Synthesis Comparative Examples. Of Synthesis Examples 14 to 19, Synthesis Examples 14 to 16 are Synthesis Examples, and Synthesis Examples 17 to 19 are Synthesis Comparative Examples. Of Examples 1 to 6, Examples 1 to 3 are Examples, and Examples 4 to 6 are Comparative Examples.

[0070] <Measurement of Unsaturation Degree of Polyether Polyol (Precursor Polymer)> The unsaturation degree of the polyether polyol (precursor polymer) was calculated according to the method described in JIS K-1557-3 (2007). The results are shown in Table 1.

[0071] <Measurement of hydroxyl value-converted molecular weight (OHV number-converted molecular weight) of polyether polyol (precursor polymer)> The "hydroxyl value-converted molecular weight (OHV number-converted molecular weight)" is a molecular weight calculated using the value obtained by applying the hydroxyl value calculated based on JIS K 1557-1 (2007) for a polyether polyol (precursor polymer) containing repeating units based on an alkylene oxide monomer to the formula "[56,100 / (hydroxyl value)] × number of active hydrogen atoms in the initiator." The results are shown in Table 1.

[0072] <Measurement of Melting Point of Initiator> The melting point of the initiator was measured by the following method. --Method for Measuring the Melting Point of the Initiator-- The melting point was calculated by differential scanning calorimetry (hereinafter referred to as DSC) in which a measurement sample was cooled to -70°C at a cooling rate of 11°C / min, held isothermally for 10 minutes, and then heated to 180°C at a heating rate of 10°C / min, repeating this procedure twice, and reading the temperature of the endothermic peak from the DSC melting curve obtained by recording the cooling and second heating curves. The measurement device used was a Netzsch DSC 3500 Sirius with a liquid nitrogen cooling system, and the measurement was carried out throughout under a nitrogen atmosphere with nitrogen gas flowing at a flow rate of 40 ml / min. The measurement sample was prepared by placing approximately 40 mg of the sample in a light aluminum pan and crimping the lid to close it.

[0073] <Measurement of Viscosity of Polyether Polyol (Precursor Polymer)> The viscosity of the polyether polyol (precursor polymer) was calculated at a measurement temperature of 25°C using an E-type viscometer (TV-22H model, manufactured by Toki Sangyo Co., Ltd.) according to the method described in JIS K 1557-5 (2007).

[0074] <Calculation of silylation rate of polyether polyol having reactive silicon groups> In the method of subjecting the hydroxyl groups of the precursor polymer to a urethane reaction with an isocyanate silane compound, the silylation rate (mol %) was defined as the charge equivalent of the isocyanate groups of the isocyanate silane compound relative to the hydroxyl groups of the precursor polymer.

[0075] <Synthesis of Polyether Polyol (Precursor Polymer)> (Synthesis Example 1) Polyglycerin (product name: PGL10PSW, manufactured by Daicel Corporation, hydroxyl value: 823 mg KOH / g, number of functional groups: 12, melting point: 12 ° C, ratio of primary hydroxyl groups to the total hydroxyl groups of the initiator: 60%) was previously dehydrated for 3 hours under conditions of 120 ° C and 5 mmHg or less and used as an initiator. To obtain 200 g of polymer in a 200 mL autoclave, 730 parts by mass of PO was subjected to ring-opening addition polymerization at 120 ° C. using 2.6 parts by mass of KOH catalyst as a ring-opening polymerization catalyst for 100 parts by mass of this initiator for an addition time of 16 hours to obtain 830 parts by mass of polyol (b). The hydroxyl value of the resulting polyol (b) was 112.0 mg KOH / g. Furthermore, 100 parts by mass of the obtained polyol (b) was used as a ring-opening polymerization catalyst using 0.2 parts by mass of a zinc hexacyanocobaltate complex (TBA-DMC catalyst) in which the ligand is t-butyl alcohol, and 408 parts by mass of PO was subjected to ring-opening addition polymerization at 130 ° C. for 5 hours to obtain 508 parts by mass of polyether polyol (precursor polymer (A-1)). The resulting polyether polyol (precursor polymer (A-1)) had a hydroxyl value-based molecular weight of 36,000, a viscosity of 5,100 mPa s, and a total unsaturation value (USV) of 0.006 meq / g.

[0076] Synthesis Example 2 Polymerization was carried out in the same manner as in Synthesis Example 1, except that the amount of PO added to the polyol (b) was 860 parts by mass and this PO was added over 8 hours, to obtain 960 parts by mass of a polyether polyol (precursor polymer (A-2)). The polyether polyol (precursor polymer (A-2)) had a hydroxyl value-based molecular weight of 68,000, a viscosity of 30,000 mPa s, and a USV of 0.006 meq / g.

[0077] (Synthesis Example 3) Polyglycerin (product name: PGL20PW, manufactured by Daicel Corporation, hydroxyl value: 724 mg KOH / g, number of functional groups: 22, melting point: 17 ° C., ratio of primary hydroxyl groups to the total hydroxyl groups of the initiator: 65%) was previously dehydrated for 3 hours under conditions of 120 ° C. and 5 mmHg or less and used as an initiator. To obtain 200 g of polymer in a 200 mL autoclave, 508 parts by mass of PO as a cyclic ether was subjected to ring-opening addition polymerization at 120 ° C. using 2.4 parts by mass of KOH catalyst as a ring-opening polymerization catalyst for 100 parts by mass of this initiator, and an addition time of 12 hours to obtain 598 parts by mass of polyol (c). The hydroxyl value of the resulting polyol (c) was 120.8 mg KOH / g. Furthermore, to obtain 200 g of polymer in a 200 mL autoclave, 378 parts by mass of PO was subjected to ring-opening addition polymerization at 130°C for 16 hours using 0.26 parts by mass of TBA-DMC catalyst as a ring-opening polymerization catalyst relative to 100 parts by mass of polyol (c), to obtain 408 parts by mass of polyether polyol (precursor polymer (A-3)). The resulting polyether polyol (precursor polymer (A-3)) had a hydroxyl value-based molecular weight of 40,000, a viscosity of 3,000 mPa s, and a USV of 0.006 meq / g.

[0078] Synthesis Example 4 Polymerization was carried out in the same manner as in Synthesis Example 3, except that the amount of PO added to the polyol (c) was 586 parts by mass and this PO was added over 5 hours, to obtain 634 parts by mass of a polyether polyol (precursor polymer (A-4)). The resulting polyether polyol (precursor polymer (A-4)) had a hydroxyl value-based molecular weight of 62,000, a viscosity of 5,400 mPa s, and a USV of 0.006 meq / g.

[0079] Synthesis Example 5 Polymerization was carried out in the same manner as in Synthesis Example 3, except that the amount of PO added to the polyol (c) was 945 parts by mass and this PO was added over 8 hours, to obtain 1,022 parts by mass of a polyether polyol (precursor polymer (A-5)). The resulting polyether polyol (precursor polymer (A-5)) had a hydroxyl value-based molecular weight of 100,000, a viscosity of 12,000 mPa s, and a USV of 0.006 meq / g.

[0080] Synthesis Example 6 Polymerization was carried out in the same manner as in Synthesis Example 3, except that the amount of PO added to the polyol (c) was 1,229 parts by mass and this PO was added over 10 hours, to obtain 1,329 parts by mass of a polyether polyol (precursor polymer (A-6)). The resulting polyether polyol (precursor polymer (A-6)) had a hydroxyl value-based molecular weight of 130,000, a viscosity of 28,000 mPa s, and a USV of 0.006 meq / g.

[0081] (Synthesis Example 7) Polyglycerin (product name: PGL X, manufactured by Daicel Corporation, hydroxyl value: 682 mg KOH / g, number of functional groups: 42, melting point: 9 ° C., ratio of primary hydroxyl groups to the total hydroxyl groups of the initiator: 62%) was previously dehydrated for 3 hours under conditions of 120 ° C. and 5 mmHg or less and used as an initiator. To obtain 200 g of polymer in a 200 mL autoclave, 100 parts by mass of this initiator was subjected to ring-opening addition polymerization using 1.5 parts by mass of KOH catalyst as a ring-opening polymerization catalyst and 361 parts by mass of PO as a cyclic ether at 120 ° C. for an addition time of 12 hours to obtain 452 parts by mass of polyol (d). The hydroxyl value of the resulting polyol (d) was 160.2 mg KOH / g. To obtain 200 g of polymer in a 200 mL autoclave, 100 parts by mass of polyol (d) was subjected to ring-opening addition polymerization using 0.24 parts by mass of TBA-DMC catalyst as a ring-opening polymerization catalyst and 794 parts by mass of PO as a cyclic ether at 130 ° C. for an addition time of 16 hours to obtain 866 parts by mass of polyether polyol (precursor polymer (A-7)). The resulting polyether polyol (precursor polymer (A-7)) had a hydroxyl value-based molecular weight of 130,000, a viscosity of 5,600 mPa s, and a USV of 0.006 meq / g.

[0082] Synthesis Example 8 Polymerization was carried out in the same manner as in Synthesis Example 7, except that the amount of PO added to the polyol (d) was 1,100 parts by mass and this PO was added over 11 hours, to obtain 1,200 parts by mass of a polyether polyol (precursor polymer (A-8)). The resulting polyether polyol (precursor polymer (A-8)) had a hydroxyl value-based molecular weight of 180,000, a viscosity of 9,200 mPa s, and a USV of 0.006 meq / g.

[0083] (Synthesis Example 9) In a 200 mL autoclave, 200 g of polymer was obtained, using sorbitol (number of functional groups: 6, melting point: 95 ° C., ratio of primary hydroxyl groups in the total hydroxyl groups of the initiator: 33%) as an initiator, 4.6 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst to 100 parts by mass of sorbitol, and 20,800 parts by mass of PO as a cyclic ether was subjected to ring-opening addition polymerization at 130 ° C. for 16 hours, to obtain 20,900 parts by mass of polyether polyol (precursor polymer (A-9)). The resulting polyether polyol (precursor polymer (A-9)) had a hydroxyl value-based molecular weight of 38,000, a viscosity of 19,000 mPa s, and a USV of 0.007 meq / g.

[0084] (Synthesis Example 10) Polyoxypropylene diol having a hydroxyl group-equivalent molecular weight of 700 (initiator: propylene glycol, number of functional groups of the initiator: 2, melting point: -50 ° C., ratio of primary hydroxyl groups in the total hydroxyl groups of the initiator: 50%) as a precursor polymer, per 100 parts of initiator, 0.1 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst to 1,600 parts by mass of PO as a cyclic ether at 130 ° C., addition time 10 hours to obtain 1700 parts by mass of polyether polyol (precursor polymer (A-10)). The hydroxyl value-equivalent molecular weight of the resulting polyether polyol (precursor polymer (A-10)) was 12,000, the viscosity was 7,000 mPa s, and the USV was 0.006 meq / g.

[0085] Synthesis Example 11 A polyether polyol (precursor polymer (A-11)) was synthesized in the same manner as in Synthesis Example 10, except that 0.15 parts by mass of TBA-DMC catalyst was used as the ring-opening polymerization catalyst and 2760 parts by mass of PO as the cyclic ether was subjected to ring-opening addition polymerization relative to 100 parts of the initiator. The resulting polyether polyol (precursor polymer (A-11)) had a hydroxyl value-based molecular weight of 20,000, a viscosity of 30,000 mPa s, and a USV of 0.008 meq / g.

[0086] (Synthesis Example 12) Polyoxypropylene triol having a hydroxyl group-equivalent molecular weight of 1,000 (initiator: glycerin, number of functional groups of the initiator: 3, melting point: 18 ° C., ratio of primary hydroxyl groups in the total hydroxyl groups of the initiator: 66%) was used as a polymerization precursor, and 100 parts by weight of the initiator was used as a ring-opening polymerization catalyst using 0.05 parts by weight of TBA-DMC catalyst. PO 900 parts by weight as a cyclic ether was subjected to ring-opening addition polymerization at 130 ° C. for 6 hours, and a polyether polyol (precursor polymer (A-12)) was obtained in an addition time of 6 hours. The hydroxyl value-equivalent molecular weight of the resulting polyether polyol (precursor polymer (A-12)) was 10,000, the viscosity was 3,000 mPa s, and the USV was 0.006 meq / g.

[0087] Synthesis Example 13 A polyether polyol (precursor polymer (A-13)) was synthesized in the same manner as in Synthesis Example 12, except that 0.12 parts by mass of TBA-DMC catalyst was used as the ring-opening polymerization catalyst and 2,300 parts by mass of PO as the cyclic ether was subjected to ring-opening addition polymerization relative to 100 parts of the initiator. The resulting polyether polyol (precursor polymer (A-13)) had a hydroxyl value-based molecular weight of 24,000, a viscosity of 24,000 mPa s, and a USV of 0.008 meq / g.

[0088] Synthesis of Polyether Polyol Having Reactive Silicon Groups and Preparation of Composition Synthesis Example 14 The polyether polyol (precursor polymer (A-2)) obtained in Synthesis Example 2 was used as the base polymer. The atmosphere inside a reactor containing the polyether polyol (precursor polymer (A-2)) was purged with nitrogen gas, and while maintaining the internal temperature at 50°C, 3-isocyanatepropyltrimethoxysilane was added so that the ratio of isocyanate groups per mole of hydroxyl groups in the polyether polyol (precursor polymer (A-2)) was 0.97 (NCO / OH molar ratio), and di-n-octyltin bis(mercaptoacetic acid isooctyl ester) (Neostan U-860, manufactured by Nitto Kasei Co., Ltd.) was added as a catalyst. The liquid temperature was raised to 80°C, maintained at that temperature, and stirred. Analysis was performed using a Fourier transform infrared spectrophotometer, and the reaction was continued until completion of the reaction between the hydroxyl groups and the isocyanate groups could be confirmed, yielding a polyether polyol (polymer (B-2)) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-2), yielding a composition containing polymer (B-2).

[0089] Synthesis Example 15 A polyether polyol (polymer (B-6)) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained in the same manner as in Synthesis Example 14, except that the polyether polyol obtained in Synthesis Example 6 (precursor polymer (A-6)) was used as the base polymer. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-6) to obtain a composition containing polymer (B-6).

[0090] Synthesis Example 16 A polymer (B-8) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained in the same manner as in Synthesis Example 14, except that the polyether polyol (precursor polymer (A-8)) obtained in Synthesis Example 8 was used as the base polymer. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-8) to obtain a composition containing polymer (B-8).

[0091] Synthesis Example 17 A polymer (B-9) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained in the same manner as in Synthesis Example 14, except that the polyether polyol (precursor polymer (A-9)) obtained in Synthesis Example 9 was used as the base polymer. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-9), to obtain a composition containing polymer (B-9).

[0092] Synthesis Example 18 A polymer (B-10) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained in the same manner as in Synthesis Example 14, except that the polyether polyol (precursor polymer (A-10)) obtained in Synthesis Example 10 was used as the base polymer. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-10) to obtain a composition containing polymer (B-10).

[0093] Synthesis Example 19 A polymer (B-12) having a urethane bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained in the same manner as in Synthesis Example 14, except that the polyether polyol (precursor polymer (A-12)) obtained in Synthesis Example 12 was used as the base polymer. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of polymer (B-12), to obtain a composition containing polymer (B-12).

[0094] [Preparation of Curable Composition] Curable compositions were prepared by adding any one of Additives 1 to 3 in Table 4 to 100 parts by mass of a composition containing Polymer (B-2), Polymer (B-6), Polymer (B-8), Polymer (B-9), Polymer (B-10), or Polymer (B-12) produced in Synthesis Examples 14 to 19. The additives used are shown below. Filler: Whiten SB: heavy calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd. Filler: Shiraenka CCR: colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd. Plasticizer: DINP: Vinicizer 90, diisononyl phthalate, manufactured by Kao Corporation Thixotropy imparting agent: Disparlon 6500: fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd. Hindered phenol-based antioxidant: IRGANOX 1010: manufactured by BASF Japan Ltd. Benzotriazole-based ultraviolet absorber: TINUVIN 326: manufactured by BASF Japan Ltd. Dehydrating agent: KBM-1003: vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Adhesion imparting agent: KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Adhesion imparting agent: KBM-403: 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Tin catalyst: U-860: di-n-octyltin bis(mercaptoacetic acid isooctyl ester), manufactured by Nitto Kasei Co., Ltd. Tin catalyst: U-810: dioctyltin laurate, manufactured by Nitto Kasei Co., Ltd. Tin catalyst: S-1: dioctyltin compound (tetravalent tin compound), reaction mixture of dioctyltin salt and orthosilicate ethyl, manufactured by Nitto Kasei Co., Ltd.

[0095] [Tensile Properties (Dumbbell) Test] Polymers (B-2), (B-6), (B-8), (B-9), (B-10), and (B-12) obtained in Synthesis Examples 14 to 19 were each blended with Additive 1 in Table 4 to form a curable composition, which was then filled into a 2 mm thick polyethylene mold, taking care to avoid air bubbles. After curing for 7 days in an atmosphere at 23°C and 50% relative humidity, the spacers were removed, and the resulting material was further cured for 7 days in an atmosphere at 50°C and 65% relative humidity to obtain a cured product. No. 3 dumbbell-shaped test specimens were punched out from the resulting cured product in accordance with JIS K 6251. The resulting test specimens were subjected to a tensile test using a Tensilon testing machine (temperature 23°C, tensile speed 500 mm / min), and the modulus at 50% elongation (M50, unit: N / mm ２ ), strength at break (Tmax, unit: N / mm ２ The results are shown in Table 3.

[0096] [Tensile Shear Property Test] An aluminum test piece (manufactured by Engineering Test Service Co., Ltd.) measuring 100 mm long x 25 mm wide x 2 mm thick and a birch test piece (manufactured by Engineering Test Service Co., Ltd.) measuring 100 mm long x 25 mm wide x 5 mm thick were prepared, the surfaces of which had been wiped with acetone and dried. In accordance with JIS K 6850:1999, a 1 mm thick spacer was placed between the two test pieces, and a curable composition containing additive 2 in Table 4 was applied to the surface of one test piece so that it measured 25 mm long x 25 mm wide x 1 mm thick. The curable composition was then attached to the surface of the other test piece and pressed to prepare a test specimen. The prepared test piece was aged for 7 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, after which the spacer was removed. The test piece was further aged and cured for 7 days in an atmosphere at a temperature of 50 ° C. and a relative humidity of 65% to obtain a test specimen. A tensile shear test was performed on each test piece using a Tensilon testing machine (temperature 23 ° C., tensile speed 5 mm / min). The maximum value of the tensile shear stress at this time was the maximum point stress (Tmax, unit: N / mm ２), and the elongation at maximum stress (Emax, unit: mm) were measured. "Shear property Emax" is an index representing flexibility and elasticity. Although it depends on the application, a value of 1.0 (mm) or more is considered usable. The peel surface of the test piece after the shear test was visually observed, and the ratio of the area of ​​the entire peel surface where the cured layer (adhesive layer) had cohesively failed and peeled was calculated to obtain the cohesive failure rate (%). In addition, the ratio of the area of ​​the entire peel surface where the adhesive layer had peeled at the interface and no resin remained on the test piece was calculated to obtain the interfacial peel rate (%). A higher cohesive failure rate indicates better adhesion. The results are shown in Table 3. The "cohesive failure rate (%)" is most preferably 100 (%). Furthermore, a smaller "interfacial peel rate (%)" is preferable, with 0 (%) being most preferable.

[0097] [Shear strength development after 10 minutes] As an index of strength development at a practical pulling speed, test pieces were prepared in the same manner as in the tensile shear property test, and after 10 minutes, the test pieces were pulled by hand in the longitudinal direction for about 5 cm over a period of about 2 seconds. "◯" indicates that sufficient strength was developed and the test piece did not peel off, "×" indicates that the test piece was uncured and peeled off immediately, and "Δ" indicates that the test piece was partially insufficiently cured and peeled off when pulled despite resistance. The results are shown in Table 3. "Shear strength development after 10 minutes" is an index that indicates whether the cured product is likely to reach a strength that is acceptable for practical use.

[0098] [Tack-free time measurement] Test pieces were prepared using a general formulation (additive 2) and a formulation (additive 3) with an adhesion time of less than 1 minute, which is intended for use as an instant adhesive. Test pieces were evaluated according to the method described in 5.19 "Tack-free time test" of JIS A 1439 (2016). A shorter time indicates a faster "surface curing speed." The results are shown in Table 3.

[0099]

[0100]

[0101]

[0102]

[0103] From the above, it was found that in Examples 1 to 3, polyether polyols having reactive silicon groups were obtained that maintained the flexibility and elasticity of the cured product while improving the surface curing rate and shear strength development.

[0104] The polyether polyol obtained by the polyether polyol production method of the present invention can be used as a raw material for sealants or adhesives such as silylated urethanes and modified silicone polymers, and as a raw material for polyurethanes such as urethane foams (rigid urethane foams, soft urethane foams), urethane prepolymers, urethane elastomers, and urethane resin-based adhesives. The reactive silicon group-containing polyether polyol obtained by the reactive silicon group-containing polyether polyol production method of the present invention can be used in curable compositions for sealants or adhesives. Specific applications of the curable compositions include sealants (e.g., elastic sealants for construction, sealants for double-glazing, rust-proofing and waterproofing sealants for glass edges, solar cell backside sealants, building sealants, ship sealants, automotive sealants, and road sealants), electrical insulating materials (insulating coatings for electric wires and cables), adhesives, coating materials, and potting materials, and are particularly suitable for applications requiring fast curing.

Claims

1. An initiator having a functionality of 8 or more and a melting point of 150° C. or less; A cyclic ether, A method for producing a polyether polyol, comprising reacting in the presence of a catalyst to produce a polyether polyol.

2. The method for producing a polyether polyol according to claim 1, wherein the polyether polyol has a hydroxyl value-based molecular weight of 20,000 or more and 500,000 or less.

3. The method for producing a polyether polyol according to claim 1 , wherein the initiator has a highly branched structure.

4. The method for producing a polyether polyol according to claim 1, wherein the ratio of primary hydroxyl groups to the total hydroxyl groups of the initiator is 50 to 95%.

5. The method for producing a polyether polyol according to claim 1 or 2, wherein the polyether polyol has a total degree of unsaturation of 0.01 meq / g or less.

6. The method for producing a polyether polyol according to claim 1 or 2, wherein the catalyst is a double metal cyanide complex catalyst.

7. The method for producing a polyether polyol according to claim 1 or 2, wherein the cyclic ether is reacted with the initiator by feeding the cyclic ether for an addition time of 4 to 60 hours.

8. The method for producing a polyether polyol according to claim 1 or 2, wherein the cyclic ether is at least one of ethylene oxide and propylene oxide.

9. The method for producing a polyether polyol according to claim 1 or 2, wherein the polyether polyol has a viscosity of 100,000 mPa·s or less at 25° C.

10. A method for producing a polyether polyol having a reactive silicon group, comprising the steps of: producing a polyether polyol having a reactive silicon group using a polyether polyol obtained by the method for producing a polyether polyol according to claim 1 or 2, A method for producing a polyether polyol having a reactive silicon group, comprising converting a hydroxyl group in the polyether polyol to a group having a reactive silicon group represented by the following formula (1) by the following (Method 1) or (Method 2). (Method 1) A method comprising: converting a hydroxyl group in the polyether polyol into a group containing an unsaturated group to obtain a polyether polyol (a); and reacting the unsaturated group in the polyether polyol (a) with a silylation agent (A) having a group reactive with the unsaturated group and a reactive silicon group represented by the following formula (1): (Method 2) The method comprises reacting a hydroxyl group of the polyether polyol with a silylating agent (B) having a group capable of reacting with the hydroxyl group and a reactive silicon group represented by the following formula (1): -SiR ａ (X) ３－ａ (1) (In formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.)

11. The method for producing a polyether polyol having a reactive silicon group according to claim 10, wherein the silylation rate of the polyether polyol having a reactive silicon group is 60 mol % or more.

12. The method for producing a polyether polyol having a reactive silicon group according to claim 10, wherein the polyether polyol having a reactive silicon group has a urethane bond.

13. The polyether polyol has a highly branched structure, a polyoxyalkylene chain, and eight or more molecular chain terminals which are hydroxyl groups, and the polyether polyol has a hydroxyl value-based molecular weight of 20,000 to 500,000.