WO2024057984A1 - Method for producing polyether polyol, method for producing polyether polyol having reactive silicon group, and polyether polyol - Google Patents

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

The present invention relates to a method for producing a polyether polyol, a method for producing a polyether polyol having a reactive silicon group, and a polyether polyol, and particularly relates to a method for producing a polyether polyol, and a polyether polyol obtained by the method. The present invention relates to a method for producing a polyether polyol having a reactive silicon group, which is used to produce a polyether polyol having a reactive silicon group, and the polyether polyol.

Polyether polyols are known to be used as raw materials for polyurethane resins and nonionic surfactants, and are also used as raw materials for curable materials by modifying the terminal hydroxyl groups. It is known that polyether polyols having reactive silicon groups are crosslinked even at room temperature through the formation of siloxane bonds accompanied by a hydrolysis reaction of the reactive silicon groups due to moisture, etc., and a rubber-like cured product is obtained. It has already been industrially produced and widely used in applications such as sealants, adhesives, and paints (see, for example, Patent Documents 1 to 3).

Japanese Patent Application Publication No. 2020-176169 Japanese Patent Application Publication No. 2009-46539 China Patent Application Publication No. 110922579

However, polyether polyols, which are useful as raw materials for polyether polyols having reactive silicon groups, generally have a viscosity that decreases when elongated to a certain molecular weight using initiators with 2 to 6 functional groups, which have been used so far. There is a problem in that the concentration rises rapidly, making stirring impossible and making synthesis difficult.

The present invention has been made in view of the above circumstances, and provides a raw material for polyether polyol having reactive silicon groups, which has improved surface curing speed and shear strength development while maintaining the flexibility and elasticity of the cured product. A method for producing a polyether polyol that easily yields a polyether polyol, and a polyether having a reactive silicon group for producing a polyether polyol having a reactive silicon group using the polyether polyol obtained by the production method. A method for producing a polyol and a polyether polyol are provided.

The present invention has the following aspects.
[1] Production of a polyether polyol by reacting an initiator with a functional group number of 8 or more and a melting point of 150°C or less and a cyclic ether in the presence of a catalyst to produce a polyether polyol. Method.
[2] The method for producing a polyether polyol according to [1] above, wherein the polyether polyol has a molecular weight in terms of hydroxyl value of 20,000 or more and 500,000 or less.
[3] The method for producing a polyether polyol according to [1] or [2] above, wherein the initiator has a highly branched structure.
[4] The method for producing a polyether polyol according to any one of [1] to [3] above, wherein the proportion of primary hydroxyl groups in the entire hydroxyl group of the initiator is 50 to 95%.
[5] The method for producing a polyether polyol according to any one of [1] to [4] above, 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 any one of [1] to [5] above, wherein the catalyst is a multimetal cyanide complex catalyst.
[7] The method for producing a polyether polyol according to any one of [1] to [6] above, wherein the cyclic ether is fed for an addition time of 4 to 60 hours and reacted with the initiator.
[8] The 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] The method for producing a polyether polyol according to any one of [1] to [8] above, wherein the polyether polyol has a viscosity at 25° C. of 100,000 mPa·s or less.
[10] Producing a polyether polyol having a reactive silicon group using the polyether polyol obtained by the method for producing a polyether polyol according to any one of [1] to [9] above. A method for producing a polyether polyol having a polyether polyol comprising converting the hydroxyl group in the polyether polyol into a group having a reactive silicon group represented by the following formula (1) by the following (method 1) or the following (method 2). A method for producing a polyether polyol having a reactive silicon group.
(Method 1)
A polyether polyol (a) is obtained by converting the hydroxyl group in the polyether polyol into a group containing an unsaturated group, and a group capable of reacting with the unsaturated group in the polyether polyol (a) and a group capable of reacting with the unsaturated group; A method of reacting a silylating agent (A) with a reactive silicon group represented by the following formula (1).
(Method 2)
A method of 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)
(However, in formula (1), R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, and X is a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer from 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 [10] above, 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 [10] or [11] above, wherein the polyether polyol having a reactive silicon group has a urethane bond.
[13] A polyether polyol that has a highly branched structure, has a polyoxyalkylene chain, and has eight or more molecular chain terminals that are hydroxyl groups, and the polyether polyol has a molecular weight in terms of hydroxyl value of 20,000 or more. 500,000, a polyether polyol.

According to the present invention, a polyether polyol that can be used as a raw material for a polyether polyol having a reactive silicon group, which has improved surface curing speed and shear strength development while maintaining flexibility and elasticity of the cured product, can be easily obtained. A method for producing a polyether polyol having a reactive silicon group, a method for producing a polyether polyol having a reactive silicon group using the polyether polyol obtained by the production method, and a polyether polyol having a reactive silicon group. can be provided.

The meanings and definitions of terms used in this specification are as follows.
The numerical range represented by "~" means a numerical range whose lower and upper limits are the numbers before and after ~.
The "active hydrogen-containing group" is at least one selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, and a sulfanyl group bonded to a carbon atom. It is the basis of seeds.
"Active hydrogen" refers to a hydrogen atom based on the active hydrogen-containing group and a hydrogen atom based on a hydroxyl group of water.
An "initiator" is a compound that has an active hydrogen-containing group.
"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.

"Oxyalkylene polymer" means a polymer having polyoxyalkylene chains formed from cyclic ether-based units.
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 the oxygen atoms in the polyoxyalkylene chain that are present in the oxyalkylene polymer. Refers to the atomic group containing the oxygen atom closest to the end of the molecule.

The term "precursor polymer" refers to a polymer before the introduction of reactive silicon groups, and is an oxyalkylene polymer in which a cyclic ether is polymerized to the active hydrogen of an initiator, and the terminal group is a hydroxyl group.
The "silylation rate" is 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 determined by NMR analysis. Furthermore, when the reactive silicon group is introduced into the terminal group of the derivative of the precursor polymer by a silylating agent, the silylation agent added to the total number of active hydrogen-containing groups and unsaturated groups of the derivative of the precursor polymer It may also be the ratio (mol %) of the number of silyl groups in the agent.
"Silylating agent" means a compound having a functional group that reacts with an active hydrogen-containing group or an unsaturated group and a reactive silicon group.
"The initiator has a highly branched structure" means that the initiator has a functional group number of 8 or more, has a branched structure, and 50% or more of the hydroxyl groups in the entire initiator are primary hydroxyl groups.

"Hydroxyl value equivalent molecular weight (OHV value equivalent molecular weight)" is calculated by calculating the hydroxyl value of the initiator or precursor polymer based on JIS K 1557 (2007), and is calculated as "56,100/(hydroxyl value) x (initiator or the number of terminal groups in the precursor polymer).

The number average molecular weight (hereinafter referred to as "Mn") and mass 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").

[Production method of polyether polyol]
The method for producing a polyether polyol of the present invention involves reacting an initiator with a functional group number of 8 or more and a melting point of 150°C or less with a cyclic ether in the presence of a catalyst to produce a polyether polyol. This is a method of manufacturing.
In addition, in the present specification, "to react an initiator with a cyclic ether" means "to react a cyclic ether (for example, in Synthesis Example 1 to be described later) with an initiator (for example, polyglycerin in Synthesis Example 1 to be described later)". This does not mean only "the direct reaction of propylene oxide)", but also "the direct reaction of the cyclic ether with the initiator", as well as "the direct reaction of the initiator with the cyclic ether". (For example, the concept includes "reacting a cyclic ether with polyol (b) in Synthesis Example 1, which will be described later)."

<Initiator>
The initiator is not particularly limited as long as it has a functional group number of 8 or more and a melting point of 150° C. or less, and examples thereof include polyglycerin, tripentaerythritol, polyvinyl alcohol, polyglycerol, and the like.
Among these, those having a highly branched structure are preferred. For example, polyglycerol having a highly branched structure includes branched polyglycerol, which has 8 or more functional groups and is more branched than linear polyglycerol (see structural formula (a) below). Branched polyglycerols include a 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). At least one selected from these is preferred, and polyglycerol dendrimers are more preferred.
The "proportion (abundance ratio) of primary hydroxyl groups among the hydroxyl groups in the entire initiator" (hereinafter also referred to as "primary conversion ratio") is measured by the following method. The primary conversion rate is determined by ¹ H-NMR after esterifying a sample with trifluoroacetic anhydride using the method described in the patent document (Japanese Unexamined Patent Publication No. 2000-344881). It can be calculated by the following formula (X) by obtaining the peak area derived from the hydroxyl group.
Primary conversion rate (%) = [a/(a+2xb)] x 100 Formula (X)
However, in the formula, a is a peak area value derived from primary hydroxyl groups around 4.3 ppm, and b is a peak area value derived from secondary hydroxyl groups around 5.2 ppm.
The "proportion (abundance ratio) of primary hydroxyl groups among the hydroxyl groups in the entire initiator" is not particularly limited, but from the viewpoint of easy terminal modification, it is preferably 50% or more, more preferably 50 to 95%, and even more preferably is 55-90%.
Note that using a saccharide that is solid at room temperature as an initiator is preferable because the reaction solution containing the initiator becomes highly viscous and polymerization cannot be carried out without using a solvent or diluent (water, glycerin). do not have.

　

　

Specific examples of commercially available initiators include (1) Polyglycerin (hyperbranched polymer (see structural formula below)) 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 hydroxyl groups of the entire initiator: 60%), (ii) PGL20PW (number of functional groups 22, degree of polymerization 20, melting point: 17°C, primary hydroxyl groups in the hydroxyl groups of the entire initiator) (abundance ratio): 65%), (iii) PGL , (2) Polyglycerin manufactured by Sakamoto Pharmaceutical Co., Ltd. (linear, number of functional groups 12, proportion (abundance ratio) of primary hydroxyl groups in the hydroxyl groups of the entire initiator: 17%), (3) IP TECH (Instrumental Polymer For example, a dendrimer (QUICK STAR) manufactured by TECHNOLOGIES, LTD.

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 in the initiator is not particularly limited as long as it is 8 or more, but it is preferably 8 to 60, more preferably 9 to 50, and still more preferably 10 to 45.
By setting the number of functional groups of the initiator to 8 or more, when a polyether polyol having a reactive silicon group is obtained, the curing speed of the polyether polyol having a reactive silicon group can be improved; By controlling the number of functional groups within a preferable range, the curing speed of the polyether polyol having reactive silicon groups can be further improved.

The melting point of the initiator is not particularly limited as long as it is 150°C or lower, but preferably -50 to 100°C, more preferably -50 to 90°C, still more preferably -20 to 70°C, particularly preferably 5 ~60°C.
By setting the melting point of the initiator to 150° C. or lower, the initiator can be easily handled and reactivity can be improved, and by setting the melting point of the initiator within a preferable range, the obtained polyester Ether polyols tend to be easier to handle.
Note that the "melting point of the initiator" here is measured in the same manner as in the examples described later.

<Cyclic ether>
Examples of the cyclic ether 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 in terms of good reactivity, and PO is more preferred.

There is no particular restriction on the addition time (feed time) when feeding the cyclic ether and reacting it with the initiator, but it is preferably 4 to 60 hours, more preferably 6 to 50 hours, since production tends to be efficient. time, more preferably 10 to 40 hours.
Note that the addition time (feed time) differs from the feed rate, which varies depending on the reaction scale, in that it does not vary depending on the reaction scale.

There is no particular limit to the amount of cyclic ether added to 100 parts by mass of the initiator, but when a polyether polyol having reactive silicon groups is obtained, the tensile properties of the cured product of the polyether polyol having reactive silicon groups are The content is preferably from 1,000 to 10,000 parts by weight, more preferably from 2,000 to 9,000 parts by weight, and even more preferably from 2,500 to 8,000 parts by weight.

<Catalyst>
As the catalyst, conventionally known catalysts can be used, such as an alkali catalyst such as KOH, a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and a porphyrin, and a composite metal cyanide complex. Catalysts, catalysts made of phosphazene compounds, and the like. These may be used alone or in combination of two or more.
Among these, multi-metal cyanide complex catalysts are preferred, since polyether polyols (precursor polymers) with a low degree of unsaturation are easily obtained. A conventionally known compound can be used as the composite metal cyanide complex catalyst, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, WO 2003/062301, WO 2004/067633, JP 2004-269776, JP 2005-15786, WO 2013/065802, and JP 2015-010162 The disclosed compounds and methods of preparation can be used.

There is no particular limit to the amount of catalyst added per 100 parts by mass of the initiator, but from the standpoint of facilitating rapid reaction, it is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 parts by mass. ~5 parts by mass.

[Polyether polyol (precursor polymer)]
The polyether polyol (precursor polymer) of the present invention has a highly branched structure, has a polyoxyalkylene chain, has eight or more molecular chain terminals that are hydroxyl groups, and has a molecular weight in terms of hydroxyl value of 20,000 to 20,000. 500,000 polyether polyol.
Note that the polyether polyol (precursor polymer) may be one produced by the method for producing polyether polyol of the present invention, or may not be produced by the method for producing polyether polyol of the present invention. good.

<Highly branched structure>
The highly branched structure of the polyether polyol (precursor polymer) is a structure derived from an initiator having a highly branched structure. This is a structure formed by a polyoxyalkylene chain derived from a cyclic ether extending from a hydroxyl group in an initiator having a highly branched structure. Polyether polyols (precursor polymers) having such a highly branched structure are sometimes called "dendrimers" or "hyperbranched polymers." A "dendrimer" or a "hyperbranched polymer" has a structure in which molecular chains extending from a branch point present at the center point have further branch points, and the number of terminals increases as the distance from the center point increases.

"Dendrimers" are highly branched polymers and oligomers, which can be in the form of collections of molecules of the same generation, so-called monodisperse assemblies, and also polydisperse assemblies. ) may be in the form of a collection of different generations.
Definitions of "dendrimer" include dense star polymers, starburst polymers, rod-shaped dendrimers, arborols, cascade molecules, cross-linked dendrimers, dendrimer aggregates. , etc. are included.

A "hyperbranched polymer" is a molecular structure that generally has a branched structure 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 their distribution is not uniform. Polymer branches can be of various types and lengths. The number of base units or monomers can be different depending on the different branching. The definition of "hyperbranched polymer" also includes bridged polymers and the like.

<Polyoxyalkylene chain>
Examples of polyoxyalkylene chains include polyoxypropylene chains, polyoxyethylene chains, poly(oxy-2-ethylethylene) chains, poly(oxy-1,2-dimethylethylene) chains, and poly(oxytetramethylene) chains. , poly(oxyethylene/oxypropylene) chain, poly(oxypropylene/oxy-2-ethylethylene) chain, and the like. 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) tend to improve the tensile properties and shear strength of polyether polyols having reactive silicon groups.・Oxypropylene) chains are preferred, and polyoxypropylene chains are more preferred.

<Molecular chain end>
The polyether polyol (precursor polymer) has eight or more molecular chain terminals that are hydroxyl groups. The molecular chain terminals, which are hydroxyl groups in the polyether polyol (precursor polymer), improve the tensile properties and shear strength of the polyether polyol having reactive silicon groups when a polyether polyol having reactive silicon groups is obtained. In terms of ease of use, the number is preferably 8 to 60, more preferably 9 to 50, and even more preferably 10 to 45.
When the polyether polyol (precursor polymer) has eight or more molecular chain terminals that are hydroxyl groups, the tack-free time of the cured product is short and the cured product has excellent deep curability.
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 of the terminal group of the polyoxyalkylene chain is a secondary hydroxyl group. The terminal hydroxyl group is a primary hydroxyl group.

There is no particular restriction on the molecular weight in terms of hydroxyl value of the polyether polyol (precursor polymer), but when a polyether polyol having reactive silicon groups is obtained, the tensile properties of the polyether polyol having reactive silicon groups are In terms of easy improvement, 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 "molecular weight in terms of hydroxyl value of the polyether polyol (precursor polymer)" herein is measured by the same method as in the examples described later.

The total unsaturation degree (USV) of the polyether polyol (precursor polymer) is not particularly limited, but from the viewpoint of easy terminal modification, it is preferably 0.01 meq/g or less, more preferably 0.001 to 0.0. 009 meq/g, more preferably 0.003 to 0.008 meq/g.
Note that the "total unsaturation degree (USV) of polyether polyol (precursor polymer)" here is measured by the same method as in the examples described later.

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 Preferably it is 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 later.

[Production method of polyether polyol having reactive silicon group]
The method for producing a polyether polyol having a reactive silicon group of the present invention is for producing a polyether polyol having a reactive silicon group using the polyether polyol obtained by the method for producing a polyether polyol of the present invention. The hydroxyl group in the polyether polyol is converted into a group having a reactive silicon group represented by the following formula (1) by the following (method 1) or the following (method 2).
The polyether polyol having a reactive silicon group produced by the method for producing a polyether polyol having a reactive silicon group of the present invention preferably has a urethane bond.
(Method 1)
A polyether polyol (a) is obtained by converting the hydroxyl group in the polyether polyol into a group containing an unsaturated group, and a group capable of reacting with the unsaturated group in the polyether polyol (a) and a group capable of reacting with the unsaturated group; A method of reacting a silylating agent (A) with a reactive silicon group represented by the following formula (1).
(Method 2)
A method of 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)
(However, in formula (1), R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, and X is a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer from 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. .)

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 a hydrocarbon group having 1 to 20 carbon atoms and a triorganosiloxy group.

Preferably, R is at least one member selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-chloroalkyl group, and a triorganosiloxy group. At least one member 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. It is more preferable that 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 more preferable. α-chloromethyl group is more preferred since the cured product has a fast curing speed. A methyl group is more preferred because it is easily available.

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, alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. 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, siloxane bonds are quickly formed, a crosslinked structure is easily formed in the cured product, and the physical properties of the cured product are likely to be good.

In the above formula (1), a is an integer from 0 to 2. When a is 2, R may be the same or different. When a is 0 or 1, X may be the same or different. Since curability becomes good, a is preferably 0.

Examples of the reactive silicon group represented by the formula (1) include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, and methyl. Examples include dimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, (α-chloromethyl)diethoxysilyl group, and the like.
Among these, trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group are preferable because they have high activity and good curability, and methyldimethoxysilyl group and trimethoxysilyl group are preferable. is more preferable.

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

The terminal group in the polyether polyol having a reactive silicon group may include a group represented by the following formula (2) or the following formula (3). X ¹ in the following formula (3) is a monovalent group represented by any of the following formulas (4) to (7).
Si ¹ in the following formula (2) and the following formulas (4) to (7) represents a reactive silicon group represented by the above formula (1). When a plurality of Si ¹ 's are present in one terminal group, they may be the same or different from each other.

In formula (2), R ¹ and R ³ each independently represent a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms present in the bonding group are carbon atoms, A hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of R ¹ and R ³ include -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ 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-, etc. .
Among these, R ¹ is preferably -CH ₂ -O-CH ₂ -, -CH ₂ O-, or -CH ₂ -, more preferably -CH ₂ -O-CH ₂ -. Furthermore, R ³ is preferably -CH ₂ - or -C ₂ H ₄ -, more preferably -CH ₂ -.

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

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.

In formula (3), R ⁵ represents a single bond or a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms present in the bonding group are carbon atoms, hydrogen atoms, It is an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the divalent bonding group for R ⁵ are the same as those for the divalent bonding group for R ¹ and R ³ above.
R ⁵ is 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.

In formula (6), R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
Examples of the monovalent hydrocarbon group for R ⁶ are the same as the monovalent hydrocarbon groups for R ² and R ⁴ above.
R ⁶ is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

R ⁷ and R ⁸ in formula (7) 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. Examples of the alkyl groups as R ⁷ and R ⁸ are the same as the examples of the alkyl groups as R ² and R ⁴ above.
It is preferable that R ⁷ and R ⁸ are both hydrogen atoms.

<Silylating agent (A)>
As the silylating agent (A), for example, a compound having both a group capable of reacting with an unsaturated group to form a bond (for example, a sulfanyl group) and the above-mentioned reactive silicon group, a hydrosilane compound (for example, HSiR _a (X) _3-a , where X, R and a are the same as in formula (1) above), and the like.
Specific examples of the silylating agent (A) include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyl Examples include dimethoxysilane, 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 since they have high activity and good curability.

The amount of the silylating agent (A) to be added is not particularly limited, but from the viewpoint of making the silylating agent react more efficiently, The amount 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, based on the number of moles of the group.

<Silylating agent (B)>
As the silylating agent (B), conventionally known isocyanate silane compounds described in JP-A No. 2011-178955 can be used, such as 1-isocyanatemethyldimethoxymethylsilane, 1-isocyanatemethyldiethoxyethylsilane, -Isocyanatepropylmethyldimethoxysilane, 3-Isocyanatepropylmethyldiethoxysilane, 3-Isocyanatepropyltrimethoxysilane, 3-Isocyanatepropyltriethoxysilane, Isocyanatemethylmethyldimethoxysilane, Isocyanatemethylmethyldiethoxysilane, Isocyanatemethyltrimethoxysilane , isocyanate methyltriethoxysilane, and the like.
Among these, 3-isocyanatepropyltrimethoxysilane is preferred because it has better reactivity.

There is no particular restriction on 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), but from the viewpoint of easy control of the terminal modification ratio, It is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, and even more preferably 0.8 to 1.2.

A method in which 1.0 or less unsaturated groups are introduced into one end group of a precursor polymer, and then the unsaturated group is reacted with a silylating agent (A), or the precursor polymer Conventionally known methods can be used for the urethanization reaction between the active hydrogen-containing group of the terminal group of the coalescence and the silylating agent (B). , JP-A-61-197631, JP-A-3-72527, JP-A-8-231707, JP-A-2011-178955, US Pat. No. 3,632,557, and US Pat. No. 4,960,844. For example, how to

In addition, after introducing an average of more than 1.0 unsaturated groups per end group to one end group of the polyether polyol (precursor polymer), the unsaturated group and the silylating agent (A) are combined. A conventionally known method can be used for the reaction.
For example, WO 2013/180203, WO 2014/192842, JP 2015-105293, JP 2015-105322, JP 2015-105323, JP 2015-105324, Described in International Publication No. 2015/080067, International Publication No. 2015/105122, International Publication No. 2015/111577, International Publication No. 2016/002907, Japanese Patent Application Publication No. 2016-216633, and Japanese Patent Application Publication No. 2017-39782. method can be used.

A method for introducing more than 1.0 unsaturated groups per end group into the terminal groups of a polyether polyol (precursor polymer) is to act on the polyether polyol (precursor polymer) with an alkali metal salt. After that, a method of reacting an epoxy compound having an unsaturated group and then reacting a halogenated hydrocarbon compound having an unsaturated group, or a method of reacting an alkali metal salt with the polyether polyol (precursor polymer), A method in which a halogenated hydrocarbon compound having a carbon-carbon triple bond is reacted is preferred.

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

Examples of the epoxy compound having an unsaturated group include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide.
Among these, allyl glycidyl ether is preferred.

As the epoxy compound having an unsaturated group, a compound represented by the following formula (8) is preferable.

In formula (8), R ¹ and R ² are the same as R ¹ and R ² in formula (2) above.

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. , etc.
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-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, 6-iodo-1- Examples include hexine.
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.

The reaction yields a derivative in which more than 1.0 unsaturated groups are introduced per one terminal group of the polyether polyol (precursor polymer). The derivative of polyether polyol (precursor polymer) may contain an unreacted active hydrogen-containing group in the terminal group.
The number of active hydrogen-containing groups contained in the derivative of polyether polyol (precursor polymer) is preferably 0.3 or less per molecule, more preferably 0.1 or less, from the viewpoint of storage stability.

The silylation rate of the polyether polyol having a reactive silicon group is not particularly limited, but it is preferably 60% or more, more preferably 60% or more, since the curability of the polyether polyol having a reactive silicon group is good. It is 70% or more, more preferably 80 to 98%.

Note that the silylation rate is calculated as follows.
(Calculation of silylation rate of polyether polyol having reactive silicon groups)
In a method of introducing an unsaturated group into the terminal group of a precursor polymer using allyl chloride and reacting a silylating agent with the unsaturated group to introduce a reactive silicon group, the unsaturated group introduced into the terminal group is The equivalent amount of the reactive silicon group of the silylating agent charged to the group is defined as the silylation rate (mol %).
In the reaction between the unsaturated group introduced into the terminal group of the precursor polymer using allyl chloride and the silylating agent, approximately 15 mol% of the unsaturated group does not react with the silylating agent due to a side reaction. Therefore, when less than 85 mol% of the unsaturated groups are reacted with the silylating agent, the charged equivalent and the silylation rate are equal.
In the method of causing a urethane reaction between the hydroxyl groups of a precursor polymer and an isocyanate silane compound, the silylation rate (mol %) is defined as the equivalent amount of the isocyanate groups of the isocyanate silane compound to the hydroxyl groups of the precursor polymer.

<Curable composition>
The curable composition is obtained by mixing a polyether polyol having reactive silicon groups and other necessary components.
The proportion of the polyether polyol having reactive silicon groups to the total mass of the curable composition is not particularly limited, but is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, even more preferably 4 to 45% by mass. It is 40% by mass. Within the above preferred range, the cured product of the curable composition has excellent elongation.

The curable composition may be a one-component type in which a polyether polyol having a reactive silicon group and all other components are mixed in advance, sealed and stored, and cured by moisture in the air after application. A two-component type may be used, in which a base composition containing a polyether polyol having a polyether polyol and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and base composition are mixed before use. A one-component curable composition is preferred because it is easy to apply.

The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the components containing water in advance, or to dehydrate them under reduced pressure during compounding and kneading.
In a two-component curable composition, the curing agent composition may contain water, and the base composition is difficult to gel even if it contains a small amount of water, but from the viewpoint of storage stability, the ingredients should be dehydrated and dried in advance. It is preferable to do so.
In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

(Other ingredients)
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, UV 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 No. 2013/180203, International Publication No. 2014/192842, International Publication No. 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.

Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to the following Examples, and various modifications can be made without departing from the gist of the present invention.
Among Synthesis Examples 1 to 13, Synthesis Examples 1 to 8 are Synthesis Examples, and Synthesis Examples 9 to 13 are Synthesis Comparative Examples.
Among Synthesis Examples 14 to 19, Synthesis Examples 14 to 16 are Synthesis Examples, and Synthesis Examples 17 to 19 are Synthesis Comparative Examples.
Among Examples 1 to 6, Examples 1 to 3 are examples, and Examples 4 to 6 are comparative examples.

<Measurement of degree of unsaturation of polyether polyol (precursor polymer)>
The degree of unsaturation of the polyether polyol (precursor polymer) was calculated by the method described in JIS K-1557-3 (2007). The results are shown in Table 1.

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

<Measurement of melting point of initiator>
The melting point of the initiator was measured by the following method.
--Method for measuring melting point of initiator--
The melting point is measured in differential scanning calorimetry (hereinafter referred to as DSC) by cooling the measurement sample to -70°C at a cooling rate of 11°C/min, holding it at the same temperature for 10 minutes, and then heating at a temperature of 10°C/min. It was calculated by repeating the operation of heating to 180° C. twice, and reading the temperature of the endothermic peak from the DSC melting curve that recorded the cooling and second heating curves. The measuring device used was a liquid nitrogen cooling system and DSC 3500 Sirius manufactured by Netzsch, and the measurements were performed under a nitrogen atmosphere in which nitrogen gas was flowed at a flow rate of 40 ml/min from beginning to end. For the measurement sample, approximately 40 mg of the sample was placed in a light aluminum pan, and the lid was crimped to close the pan.

<Measurement of viscosity of polyether polyol (precursor polymer)>
According to the method described in JIS K 1557-5 (2007), the viscosity of polyether polyol (precursor polymer) was measured at a measurement temperature of 25°C using an E-type viscometer (Model TV-22H, manufactured by Toki Sangyo Co., Ltd.). was calculated.

<Calculation of silylation rate of polyether polyol having reactive silicon groups>
In the method of causing a urethanization reaction between the hydroxyl groups of the precursor polymer and the isocyanate silane compound, the silylation ratio (mol %) was defined as the equivalent amount of the isocyanate groups of the isocyanate silane compound to the hydroxyl groups of the precursor polymer.

<Synthesis of polyether polyol (precursor polymer)>
(Synthesis example 1)
Polyglycerin (product name: PGL10PSW, manufactured by Daicel Corporation, hydroxyl value: 823 mgKOH/g, number of functional groups: 12, melting point: 12°C, proportion of primary hydroxyl groups in the hydroxyl groups of the entire initiator: 60%) was heated at 120°C in advance. It was dehydrated for 3 hours under conditions of 5 mmHg or less and used as an initiator.
To obtain 200 g of polymer in a 200 mL autoclave, 2.6 parts by mass of KOH catalyst was added to 100 parts by mass of this initiator, and 730 parts by mass of PO was added as a ring-opening polymerization catalyst at 120° C. for 16 hours. Ring-opening addition polymerization was performed to obtain 830 parts by mass of polyol (b). The obtained polyol (b) had a hydroxyl value of 112.0 mgKOH/g.
Furthermore, based on 100 parts by mass of the obtained polyol (b), 0.2 parts by mass of a zinc hexacyanocobaltate complex (TBA-DMC catalyst) whose ligand is t-butyl alcohol was used as a ring-opening polymerization catalyst. Then, 408 parts by mass of PO was subjected to ring-opening addition polymerization at 130° C. for an addition time of 5 hours to obtain 508 parts by mass of polyether polyol (precursor polymer (A-1)). The obtained polyether polyol (precursor polymer (A-1)) had a hydroxyl value equivalent molecular weight of 36,000, a viscosity of 5,100 mPa·s, and a total unsaturation degree (USV) of 0.006 meq/g. Ta.

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

(Synthesis example 3)
Polyglycerin (product name: PGL20PW, manufactured by Daicel Corporation, hydroxyl value: 724 mgKOH/g, number of functional groups: 22, melting point: 17°C, proportion of primary hydroxyl groups in the hydroxyl groups of the entire initiator: 65%) was preliminarily heated at 120°C. It was dehydrated for 3 hours under conditions of 5 mmHg or less and used as an initiator.
To obtain 200 g of polymer in a 200 mL autoclave, 2.4 parts by mass of KOH catalyst was used as a ring-opening polymerization catalyst and 8 parts by mass of PO50 as a cyclic ether were added at 120° C. to 100 parts by mass of this initiator. Ring-opening addition polymerization was carried out for an addition time of 12 hours to obtain 598 parts by mass of polyol (c). The hydroxyl value of the obtained polyol (c) was 120.8 mgKOH/g.
Furthermore, to obtain 200 g of polymer in a 200 mL autoclave, 378 parts by mass of PO was added to 100 parts by mass of polyol (c) at 130°C using 0.26 parts by mass of TBA-DMC catalyst as a ring-opening polymerization catalyst. Ring-opening addition polymerization was carried out for an addition time of 16 hours to obtain 408 parts by mass of polyether polyol (precursor polymer (A-3)). The obtained polyether polyol (precursor polymer (A-3)) had a molecular weight in terms of hydroxyl value of 40,000, a viscosity of 3,000 mPa·s, and a USV of 0.006 meq/g.

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

(Synthesis example 5)
Polymerization was carried out in the same manner as in Synthesis Example 3, except that the amount of PO added to polyol (c) was 945 parts by mass, and this PO was added over 8 hours. ) 1022 parts by mass were obtained. The obtained polyether polyol (precursor polymer (A-5)) had a molecular weight in terms of hydroxyl value of 100,000, a viscosity of 12,000 mPa·s, and a USV of 0.006 meq/g.

(Synthesis example 6)
Polymerization was carried out in the same manner as in Synthesis Example 3, except that the amount of PO added to polyol (c) was 1229 parts by mass, and this PO was added over 10 hours. ) 1329 parts by mass were obtained. The obtained polyether polyol (precursor polymer (A-6)) had a molecular weight in terms of hydroxyl value of 130,000, a viscosity of 28,000 mPa·s, and a USV of 0.006 meq/g.

(Synthesis example 7)
Polyglycerin (product name: PGL , dehydrated for 3 hours under conditions of 5 mmHg or less, and used as an initiator.
To obtain 200 g of polymer in a 200 mL autoclave, 1.5 parts by mass of KOH catalyst was used as a ring-opening polymerization catalyst and 1.5 parts by mass of PO3 as a cyclic ether was added at 120° C. to 100 parts by mass of this initiator. Ring-opening addition polymerization was carried out for an addition time of 12 hours to obtain 452 parts by mass of polyol (d). The hydroxyl value of the obtained polyol (d) was 160.2 mgKOH/g.
To obtain 200 g of polymer in a 200 mL autoclave, 0.24 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst, and 130 parts by mass of PO794 as a cyclic ether was added to 100 parts by mass of polyol (d). ℃, ring-opening addition polymerization was carried out for an addition time of 16 hours to obtain 866 parts by mass of polyether polyol (precursor polymer (A-7)). The obtained polyether polyol (precursor polymer (A-7)) had a molecular weight in terms of hydroxyl value of 130,000, a viscosity of 5,600 mPa·s, and a USV of 0.006 meq/g.

(Synthesis example 8)
The polyether polyol (precursor polymer (A- 8)) 1,200 parts by mass were obtained. The obtained polyether polyol (precursor polymer (A-8)) had a molecular weight in terms of hydroxyl value of 180,000, a viscosity of 9,200 mPa·s, and a USV of 0.006 meq/g.

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

(Synthesis example 10)
Polyoxypropylene diol (initiator: propylene glycol, number of functional groups in initiator: 2, melting point: -50°C, ratio of primary hydroxyl groups to hydroxyl groups in the entire initiator: 50%) with a molecular weight of 700 in terms of hydroxyl group is used as a precursor. As for coalescence, 1,600 parts by mass of PO as a cyclic ether was added to 100 parts of initiator and 0.1 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst at 130°C for an addition time of 10 hours. Addition polymerization was performed to obtain 1700 parts by mass of polyether polyol (precursor polymer (A-10)). The resulting polyether polyol (precursor polymer (A-10)) had a hydroxyl value equivalent molecular weight of 12,000, a viscosity of 7,000 mPa·s, and a USV of 0.006 meq/g.

(Synthesis example 11)
Polymer was produced in the same manner as in Synthesis Example 10, except that 0.15 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst and 760 parts by mass of PO2 as a cyclic ether was used for ring-opening addition polymerization with respect to 100 parts of initiator. An ether polyol (precursor polymer (A-11)) was synthesized. The resulting polyether polyol (precursor polymer (A-11)) had a hydroxyl value equivalent molecular weight of 20,000, a viscosity of 30,000 mPa·s, and a USV of 0.008 meq/g.

(Synthesis example 12)
Polyoxypropylene triol (initiator: glycerin, number of functional groups in initiator: 3, melting point: 18°C, ratio of primary hydroxyl groups to hydroxyl groups in the entire initiator: 66%) with a hydroxyl group equivalent molecular weight of 1,000 is used as a polymerization precursor. As a ring-opening polymerization catalyst, 900 parts by mass of PO as a cyclic ether was added to 100 parts of initiator and 0.05 parts by mass of TBA-DMC was used as a ring-opening polymerization catalyst at 130°C for an addition time of 6 hours. Thus, 1700 parts by mass of polyether polyol (precursor polymer (A-12)) was obtained. The obtained polyether polyol (precursor polymer (A-12)) had a molecular weight in terms of hydroxyl value of 10,000, a viscosity of 3,000 mPa·s, and a USV of 0.006 meq/g.

(Synthesis example 13)
Same as Synthesis Example 12 except that 0.12 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst and 2,300 parts by mass of PO as a cyclic ether was used for ring-opening addition polymerization with respect to 100 parts of initiator. A polyether polyol (precursor polymer (A-13)) was synthesized. The resulting polyether polyol (precursor polymer (A-13)) had a hydroxyl value equivalent molecular weight of 24,000, a viscosity of 24,000 mPa·s, and a USV of 0.008 meq/g.

<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 a base polymer. The interior of the reactor containing the polyether polyol (precursor polymer (A-2)) was replaced with nitrogen gas, and while the internal temperature was maintained at 50°C, the polyether polyol (precursor polymer (A-2)) was heated. 3-Isocyanatepropyltrimethoxysilane was added so that the ratio of isocyanate groups to 1 mole of hydroxyl groups was 0.97 (NCO/OH molar ratio). ) (Neostan U-860, manufactured by Nitto Kasei Co., Ltd.) was added. The liquid temperature was raised to 80°C, maintained, and stirred. The reaction was performed until the completion of the reaction between hydroxyl groups and isocyanate groups was confirmed by analysis using a Fourier transform infrared spectrophotometer, and the result was a polyether polyol (polyether polyol) with urethane bonds in the main chain and trimethoxysilyl groups introduced into the terminal groups. Combined product (B-2)) was obtained. As a storage stabilizer, 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of polymer (B-2). ) was obtained.

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

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

(Synthesis example 17)
A urethane bond was added to the main chain and trimethoxysilyl was added to the terminal group 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. A polymer (B-9) into which groups were introduced was obtained. As a storage stabilizer, 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of the polymer (B-9). 9) was obtained.

(Synthesis example 18)
A urethane bond was added to the main chain and trimethoxysilyl was added to the terminal group 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. A polymer (B-10) into which groups were introduced was obtained. As a storage stabilizer, 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of the polymer (B-10). 10) was obtained.

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

[Preparation of curable composition]
Polymer (B-2), polymer (B-6), polymer (B-8), polymer (B-9), polymer (B-10) or polymer produced in Synthesis Examples 14 to 19 above A curable composition was prepared by adding any one of additives 1 to 3 in Table 4 to 100 parts by mass of the composition containing aggregate (B-12).
The additives used are shown below.
Filler: Whiten SB: Heavy calcium carbonate, manufactured by Shiroishi Industries Co., Ltd. Filler: White Glossy CCR: Colloidal calcium carbonate, manufactured by Shiroishi Industries Co., Ltd. Plasticizer: DINP: Vinicizer 90, diisononyl phthalate, manufactured by Kao Corporation Thixotropic properties Agent: Disparon 6500: Fatty acid amide wax, manufactured by Kusumoto Kasei Co., Ltd. Hindered phenolic antioxidant: IRGANOX1010: Made by BASF Japan Co., Ltd. Benzotriazole ultraviolet absorber: TINUVIN326: Made by BASF Japan Co., Ltd. Dehydrating agent: KBM-1003: Vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Adhesive agent: KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Adhesive 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, Nitto Kasei Co., Ltd. Tin catalyst: S-1: Dioctyltin compound (tetravalent tin compound), reaction mixture of dioctyltin salt and orthoethyl silicate, Nitto Kasei Co., Ltd.

[Tensile properties (dumbbell) test]
Polymer (B-2), polymer (B-6), polymer (B-8), polymer (B-9), polymer (B-10) and polymer obtained in Synthesis Examples 14 to 19 For each of the composites (B-12), a curable composition containing Additive 1 shown in Table 4 was filled into a polyethylene mold having a thickness of 2 mm so as to prevent air bubbles from entering. After curing for 7 days in an atmosphere with a temperature of 23° C. and a relative humidity of 50%, the spacer was removed, and further curing was carried out for 7 days in an atmosphere with a temperature of 50° C. and a relative humidity of 65% to obtain a cured product. A No. 3 dumbbell-shaped test piece was punched out from the obtained cured product in accordance with JIS K 6251. The obtained test piece was subjected to a tensile test using a Tensilon tester (temperature 23°C, tensile speed 500 mm/min), and the modulus at 50% elongation (M50, unit: N/mm ² ) and strength at break (Tmax , unit: N/mm ² ) and elongation at break (E, unit: %) were measured. The results are shown in Table 3.

[Tensile shear property test]
A 100 mm long x 25 mm wide x 2 mm thick aluminum test piece (manufactured by Engineering Test Service Co., Ltd.) whose surface was wiped with acetone and dried, and a birch wood test piece (100 mm long x 25 mm wide x 5 mm thick) (manufactured by Engineering Test Service Co., Ltd.). (Manufactured by Engineering Test Service Co., Ltd.) was prepared, and a spacer with a thickness of 1 mm was placed between the two test pieces in accordance with JIS K 6850:1999, resulting in a test piece measuring 25 mm in length x 25 mm in width x 1 mm in thickness. A curable composition containing Additive 2 in Table 4 was applied to the surface of one test piece, and the test piece was laminated and pressure-bonded to the surface of the other test piece to prepare a test piece. The prepared test specimen was cured for 7 days in an atmosphere with a temperature of 23°C and a relative humidity of 50%, the spacer was removed, and then cured for 7 days in an atmosphere with a temperature of 50°C and a relative humidity of 65% to harden it. A test piece was obtained.
A tensile shear test was conducted on each test piece using a Tensilon tester (temperature: 23° C., tensile speed: 5 mm/min). As the maximum value of the tensile shear stress at this time, the maximum point stress (Tmax, unit: N/mm ² ) and the elongation at the maximum stress (Emax, unit: mm) were measured. "Shear property Emax" is an index representing flexibility and elasticity. Although it depends on the purpose, if it is 1.0 (mm) or more, it is at a usable level.
The peeled surface of the test piece after the shear test was visually observed, and the ratio of the area where the cured material layer (adhesive layer) was cohesively failed and peeled off on the entire peeled surface was calculated as the cohesive failure rate (%). . In addition, the ratio of the area where the adhesive layer was peeled off at the interface and no resin remained on the test piece with respect to the entire peeled surface was calculated and defined as the interfacial peeling rate (%). The higher the cohesive failure rate, the better the adhesiveness. The results are shown in Table 3. The "cohesive failure rate (%)" is most preferably 100 (%). Further, the "interface peeling rate (%)" is preferably smaller, and most preferably 0 (%).

[Shear strength development after 10 minutes]
As an indicator of strength development at a practical tensile speed, a test piece was prepared in the same manner as the tensile shear property test, and after 10 minutes, the test piece was manually pulled about 5 cm in the longitudinal direction for about 2 seconds. "〇" indicates that the strength is sufficient and does not peel off, "x" indicates that it was uncured and could be easily peeled off, and "△" indicates that some parts were not sufficiently cured and there was no resistance. Although it was attached, it peeled off when pulled. The results are shown in Table 3. "Development of shear strength after 10 minutes" is an index showing whether the cured product easily reaches a strength that does not cause any problems in practical use.

[Tack free time measurement]
Test specimens were prepared using a general formulation (Additive 2) and a formulation (Additive 3) with a bonding time of 1 minute or less, which is assumed to be used as an instant adhesive. Evaluation was made in accordance with the method described in No. 19 "Touch Dry Time Test". The shorter the time, the faster the "surface curing speed." The results are shown in Table 3.

From the above, it was found that in Examples 1 to 3, polyether polyols having reactive silicon groups were obtained that exhibited improved surface curing speed and shear strength development while maintaining the flexibility and elasticity of the cured products. .

The polyether polyol obtained by the method for producing polyether polyol of the present invention can be used as raw materials for sealants or adhesives such as silylated urethane and modified silicone polymer, urethane foam (rigid urethane foam, flexible urethane foam), urethane prepolymer, It can be used as a raw material for polyurethane such as urethane elastomers and urethane resin adhesives.
The polyether polyol having a reactive silicon group obtained by the method for producing a polyether polyol having a reactive silicon group of the present invention can be used in a curable composition for sealants or adhesives. Specific uses of the curable composition include sealing materials (e.g., elastic sealing materials for construction, sealing materials for double-glazed glass, sealing materials for rust prevention and waterproofing of glass edges, sealing materials for the back side of solar cells, construction materials, etc.). Suitable are sealants for objects, sealants for ships, sealants for automobiles, sealants for roads), electrical insulation materials (insulation coating materials for electric wires and cables), adhesives, coating materials, and potting materials. Ideal for applications that require hardenability.

Claims (13)

an initiator having a functional group number of 8 or more and a melting point of 150° C. or less;
cyclic ether,
A method for producing a polyether polyol, which comprises producing a polyether polyol by reacting in the presence of a catalyst. The method for producing a polyether polyol according to claim 1, wherein the polyether polyol has a molecular weight in terms of hydroxyl value of 20,000 or more and 500,000 or less. The method for producing a polyether polyol according to claim 1, wherein the initiator has a highly branched structure. The method for producing a polyether polyol according to claim 1, wherein the proportion of primary hydroxyl groups in the total hydroxyl groups of the initiator is 50 to 95%. The method for producing a polyether polyol according to claim 1 or 2, wherein the total unsaturation degree of the polyether polyol is 0.01 meq/g or less. The method for producing a polyether polyol according to claim 1 or 2, wherein the catalyst is a multimetal cyanide complex catalyst. The method for producing a polyether polyol according to claim 1 or 2, wherein the cyclic ether is fed for an addition time of 4 to 60 hours to react with the initiator. 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. 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. A method for producing a polyether polyol having a reactive silicon group, the method comprising producing a polyether polyol having a reactive silicon group using the polyether polyol obtained by the method for producing a polyether polyol according to claim 1 or 2. hand,
A polyether polyol having a reactive silicon group, which converts the hydroxyl group in the polyether polyol into a group having a reactive silicon group represented by the following formula (1) by the following (method 1) or the following (method 2). manufacturing method.
(Method 1)
A polyether polyol (a) is obtained by converting the hydroxyl group in the polyether polyol into a group containing an unsaturated group, and a group capable of reacting with the unsaturated group in the polyether polyol (a) and a group capable of reacting with the unsaturated group; A method of reacting a silylating agent (A) with a reactive silicon group represented by the following formula (1).
(Method 2)
A method of 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)
(However, in formula (1), R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, and X is a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer from 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. .) 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. The method for producing a polyether polyol having a reactive silicon group according to claim 10 or 11, wherein the polyether polyol having a reactive silicon group has a urethane bond. A polyether polyol having a highly branched structure, having a polyoxyalkylene chain, and having eight or more molecular chain terminals that are hydroxyl groups, wherein the polyether polyol has a molecular weight in terms of hydroxyl value of 20,000 to 500,000. A polyether polyol.