JP7586368B1 - Method for producing polyether compound - Google Patents

Abstract

The present invention provides a method for producing a polyether compound, which can reliably produce a polyether compound having a narrow molecular weight distribution and low viscosity.
[Solution] In a method for producing a polyether compound, an initiator having active hydrogen is contacted with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator, and the methanol content of the alkylene oxide-containing raw material is 0.0001 ppm or more and less than 20 ppm based on the total mass of the alkylene oxide-containing raw material.
[Selection diagram] None

Description

The present invention relates to a method for producing a polyether compound.

Polyether compounds are used as raw materials for adhesives, paints, sealants, etc. Polyether compounds are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

Patent Document 1 discloses a method for producing a hydrolyzable silyl group-containing polyoxyalkylene, which includes a step of ring-opening polymerizing a monoepoxide having a water content of 5 ppm or more and less than 50 ppm to obtain a hydroxyl group-containing polyoxyalkylene, and a step of introducing a hydrolyzable silyl group into the hydroxyl group-containing polyoxyalkylene. It discloses that by using a monoepoxide with a low water content, the obtained hydrolyzable silyl group-containing polyoxyalkylene can exhibit a high modulus after curing.

International Publication No. 2023/095636

However, according to the inventor's research, even when a composite metal cyanide complex catalyst is used, the molecular weight distribution of the polyether compound may not be sufficiently narrow. If the molecular weight distribution is broad, the viscosity of the polyether compound increases, which may result in poor workability.

The objective of the present invention is to provide a manufacturing method that can reliably produce polyether compounds with narrow molecular weight distribution and low viscosity.

The present invention has the following aspects.
[1] A method for producing a polyether compound, comprising the steps of:
contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator;
The alkylene oxide-containing feedstock has a methanol content of 0.0001 ppm or more and less than 20 ppm, based on the total mass of the alkylene oxide-containing feedstock.
[2] The method according to [1], wherein the alkylene oxide content of the alkylene oxide-containing raw material is 99.70 mass% or more.

The present invention provides a method for producing polyether compounds that can more reliably produce polyether compounds with narrow molecular weight distribution and low viscosity.

The meanings and definitions of terms used in this specification are as follows:
The numerical range expressed by "-" means that the numerical values before and after "-" are the lower and upper limits of the numerical range.

The "unit" constituting a polyether compound or the like means an atomic group formed directly by polymerization of a monomer.
The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the polyether compounds, polyether compounds having a reactive silicon group, and polyether compounds having a polymerizable unsaturated group described below, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion including a repeating unit based on an alkylene oxide (polyoxyalkylene chain).
The polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group are polymers consisting of a main chain and terminal groups.
The "end group" of the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group means an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, when the atomic group contains a residue of an initiator, it is not considered as an end group, but as a part of the main chain. The "number of end groups" in the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group is the same number as the number of active hydrogens of the initiator described below.
The "active hydrogen-containing group" refers to 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 obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group.
The term "active hydrogen" refers to a hydrogen atom derived from the above active hydrogen-containing group and a hydrogen atom derived from a hydroxyl group of water.

The "silylation rate" of a polyether compound having a reactive silicon group is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, hydroxyl groups, unsaturated groups, and isocyanate groups in the terminal groups of the polyether compound having a reactive silicon group. Specifically, the silylation rate is calculated by the following formula:
Silylation rate (%)=100×number of reactive silicon groups/[number of reactive silicon groups+number of hydroxyl groups+number of isocyanate groups+(number of carbon-carbon double bonds)+(number of carbon-carbon triple bonds)×2]
The value of the silylation rate can be measured by NMR analysis. It may also be the ratio (mol%) of the number of silyl groups of the silylating agent added to the number of terminal groups when the reactive silicon group is introduced into the terminal group of the polyether compound by the silylating agent described later. However, in this case, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described later.
The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group.
The content of isocyanate groups relative to the total mass of the prepolymer described below is a value measured in accordance with JIS K 7301:1995.

The number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification are polystyrene-equivalent molecular weights measured using GPC (Gel Permeation Chromatography) with tetrahydrofuran as the eluent, and a calibration curve created using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw/Mn) is the ratio of Mw to Mn.

The "hydroxyl value" of the polyether compound is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007.
The hydroxyl value-based molecular weight is a value calculated by: 56,100/hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound (number of active hydrogens of initiator). When two or more polyether compounds having different numbers of hydroxyl groups are contained, the number of hydroxyl groups of the polyether compound is the average number of hydroxyl groups.

The degree of unsaturation of the polyether compound can be measured in accordance with JIS K 1557-3:2007.
The viscosity of the polyether compound is measured using an E-type viscometer.
The ultra-high molecular weight component of a polyether compound means a component having a molecular weight ranging from 12 times (12W) to 46 times (46W) the Mn of a polyether compound, where W is the molecular weight.
The content of ultrahigh molecular weight components is measured by the method described in JP 2019-137810 A.

The methanol content and the alkylene oxide content of the alkylene oxide-containing raw material are measured by gas chromatography, as described in detail in the Examples.
"ppm" is by mass unless otherwise specified.

<Production method of polyether compound>
In the method for producing a polyether compound of the present embodiment, an initiator having active hydrogen is contacted with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator.

<Alkylene oxide-containing raw material>
The alkylene oxide (hereinafter, also referred to as "AO") is selected depending on the constituent units of the polyoxyalkylene chain of the polyether compound to be produced.
Examples of AO include ethylene oxide (hereinafter also referred to as "EO"), propylene oxide (hereinafter also referred to as "PO"), 1,2-butylene oxide, and 2,3-butylene oxide.
From the viewpoint of suppressing the generation of ultra-high molecular weight components, the AO is preferably an AO having 3 or more carbon atoms. As the AO having 3 or more carbon atoms, an AO having 3 to 5 carbon atoms is preferable, and PO is more preferable.
The AO contained in the AO-containing raw material may be one type or two or more types.

The AO-containing raw material may contain, in addition to AO, components other than AO (hereinafter also referred to as "impurities").
The crude product obtained in the synthesis reaction of AO contains impurities. Usually, the crude product is purified, but some impurities remain even after the purification process. Furthermore, the impurity content may vary depending on the lot, even for the same product.
The impurities may vary depending on the synthesis method of AO, but examples of the impurities include water, aldehydes, acids, methanol, methyl formate, and chlorine. Examples of the aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. The impurities contained in the AO-containing raw material may be one type or two or more types.

The methanol content of the AO-containing raw material is 0.0001 ppm or more and less than 20 ppm, more preferably 0.001 ppm or more and less than 19 ppm, and even more preferably 0.01 ppm or more and less than 18 ppm, based on the total mass of the AO-containing raw material. If the methanol content is equal to or less than the upper limit, the catalyst toxicity of the AO-containing raw material is reduced, and the molecular weight distribution of the polyether compound is narrowed. If the methanol content is equal to or more than the lower limit, the molecular weight distribution of the polyether compound is narrowed. This is presumably because methanol functions as a chain transfer agent in the polymerization reaction, making it easier to obtain polyether compounds with uniform molecular weights.

The AO content (purity) of the AO-containing raw material is preferably 99.70% by mass or more, more preferably 99.75% by mass or more, and even more preferably 99.80% by mass or more, based on the total mass of the AO-containing raw material. When the AO-containing raw material is equal to or more than the above lower limit, a polyether compound having a narrow molecular weight distribution and low viscosity can be more reliably obtained.
The total content of AO and impurities does not exceed 100 mass % based on the total mass of the AO-containing raw material.

The AO-containing raw material may be selected from commercially available AO-containing raw materials having an impurity content within a desired range, or may be produced by a known production method.
For example, the target AO-containing raw material may be obtained by synthesizing AO by a known method and adjusting the impurity content of the obtained crude product containing AO. The target AO-containing raw material may be obtained by adjusting the impurity content of a commercially available AO-containing raw material.
Examples of methods for synthesizing AO include the chlorohydrin method, the organic peroxide method, and the hydrogen peroxide method (HPPO method).
Examples of the method for adjusting the impurity content include a method for reducing the impurity content by a purification treatment and a method for adding impurities. Examples of the purification treatment include washing with water and drying.

The type and content of impurities in the crude product or AO-containing raw material can be adjusted by the AO synthesis method and purification treatment conditions.
For example, among the above-mentioned methods for synthesizing AO, the crude product obtained by the chlorohydrin method generally contains impurities such as aldehydes, acids, methanol, and chlorine, but does not contain methyl formate, whereas the crude product obtained by the hydrogen peroxide method generally contains impurities such as aldehydes, acids, methanol, and methyl formate, but does not contain chlorine.

<Initiator>
The number of active hydrogens in the initiator is preferably 1 or more, more preferably 2 to 10, further preferably 2 to 8, and particularly preferably 2 to 6. The number of active hydrogens in the initiator is preferably selected according to the number of hydroxyl groups per molecule of the polyether compound to be obtained. The number of active hydrogens in the initiator and the number of terminal groups in the polyether compound are the same.
The initiators may be used alone or in combination of two or more.

The initiator preferably has a hydroxyl group as the active hydrogen-containing group.
As the initiator having one hydroxyl group, a monohydric alcohol having a linear or branched hydrocarbon group is preferable, specifically, methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol can be mentioned.
Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol.
Water is also an example of an initiator having two hydroxyl groups.
Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane.
Examples of initiators having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, and diglycerin.
Alternatively, a low molecular weight polymer obtained by polymerizing an alkylene oxide with these initiators in the presence of an alkali metal hydroxide may be used as the initiator.
The hydroxyl value of the initiator is, for example, preferably from 3 to 842 mgKOH/g, and more preferably from 7 to 561 mgKOH/g.

<Double metal cyanide complex catalyst>
A composite metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxide. The DMC catalyst is a crystalline solid, and contains a reaction product of a metal halide salt and a transition metal cyanide compound, an organic ligand, and crystal water (coordination water, etc.) contained in the crystal. In addition, it may contain impurities that are unavoidable in the production and moisture other than crystal water that are contained in trace amounts in the metal salt and metal compound.
The metal halide salt, transition metal cyanide compound, and organic ligand that can be used are those known in the production of DMC catalysts.

The DMC catalyst is believed to be represented by Formula 1 below.
M ¹ _a [M ² (CN) _b ] _c・d(M ¹ _e X _f )・g(Ligand)・h(H ₂ O) Formula 1
In formula 1, M ¹ _e X _f is a metal halide salt, M ¹ is a metal atom that serves as a cation, X is a halogen atom that serves as a counter anion, M ² is a transition metal atom contained in a transition metal cyanide compound that serves as an active site, and Ligand is an organic ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c, e, and f are electrically neutral numbers.

Examples of ^M1 include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV) and W(VI).
Examples of ^M2 include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V).
Examples of X include Cl, Br and I.
The metal halide salt of M ¹ _e X _f is preferably at least one selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate, and more preferably at least one selected from zinc chloride and zinc bromide in terms of the interatomic distance between M ² and X described later.
Examples of the Ligand (organic ligand) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles and sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. The organic ligand may be one type or two or more types. Examples of the alcohol include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. Examples of the polyoxyalkylene poly(or mono)ol include polypropylene diol. As the organic ligand, tert-butyl alcohol is preferable.

A preferred example of a DMC catalyst is zinc hexacyanocobaltate ( _Zn3 [Co(CN) ₆ ] ₂ ) containing an organic ligand (Ligand), water, zinc chloride or zinc bromide. Its chemical formula is considered to be _Zn3 [Co(CN) ₆ ] _2.d ( _ZnCl2 ).g(Ligand).h( _H2O ) or _Zn3 [Co(CN) ₆ ] _2.d ( _ZnBr2 ).g(Ligand).h( _H2O ).

The DMC catalyst is preferably a zinc hexacyanocobaltate (Zn ₃ [Co(CN) ₆ ] ₂ ) complex with tert-butyl alcohol as the ligand, which may also be coordinated with water and zinc chloride.

The DMC catalyst may be used, for example, in the production of polyether compounds in a solid state, or in the production of polyether compounds in a slurry state in which DMC catalyst particles are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst").

The slurry catalyst includes a DMC catalyst and a dispersion medium.
The slurry catalyst is preferably a slurry that contains a DMC catalyst and a dispersion medium, and may also contain impurities and moisture that are unavoidable during production.

As the dispersion medium of the slurry catalyst, an organic solvent known in the art for slurry catalysts can be used. For example, the hardly volatile hydroxy compound described in Japanese Patent No. 3194255 can be used. The hydroxy compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and a compound having an alcoholic hydroxyl group such as a polyether compound is preferred.
As the dispersion medium for the slurry catalyst, a polyether compound is preferred since it does not become an impurity in the product (polyether compound) of the polymerization of the alkylene oxide.
The Mn of the polyether compound used as the dispersion medium is preferably 100 to 8000, more preferably 600 to 3000. When Mn is equal to or more than the lower limit, it does not become a catalyst poison, and when it is equal to or less than the upper limit, the handleability of the slurry catalyst is excellent.
Furthermore, an initiator used in polymerizing the alkylene oxide may be used as a part of the dispersion medium.

The dispersion medium of the slurry catalyst preferably does not substantially contain water. Specifically, the water content of the dispersion medium is preferably 500 ppm or less, more preferably 200 ppm or less, and may be an undetectable amount.
The water content of the dispersion medium is the water content measured by the Karl Fischer measurement method.

The content of the DMC catalyst relative to the total mass of the slurry catalyst is, for example, preferably 0.001 to 60 mass %, more preferably 0.003 to 50 mass %, and even more preferably 0.006 to 30 mass %.
In particular, when the dispersion medium is a polyether compound, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 1 to 60 mass %, more preferably 3 to 40 mass %, and even more preferably 5 to 30 mass %.
In particular, when the dispersion medium contains the initiator, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.003 to 0.02 mass%, more preferably 0.004 to 0.015 mass%, and even more preferably 0.006 to 0.01 mass%.

The DMC catalyst can be produced by a known method.
For example, a DMC catalyst is synthesized by reacting a metal halide salt with a transition metal cyanide compound to obtain a reaction product, and then coordinating an organic ligand with the reaction product. After synthesizing the DMC catalyst, the water content of the DMC catalyst may be adjusted.

A metal halide salt and a transition metal cyanide compound are reacted in the presence of water to obtain a reaction product, and an organic ligand is coordinated in the presence of water to obtain a mixed liquid containing a DMC catalyst and water. Impurities and water may be removed from the resulting mixed liquid, and the moisture content of the resulting solid may be reduced to a predetermined range to obtain a DMC catalyst.

As a preferred embodiment of the method for producing the DMC catalyst, for example, the following method can be mentioned.
First, an aqueous solution of a metal halide salt is reacted with an aqueous solution of a transition metal cyanide compound to generate a reaction product. An aqueous solution of an organic ligand is added to the reaction product and stirred to coordinate the organic ligand, thereby obtaining a mixed solution containing a DMC catalyst and water. The resulting mixed solution is subjected to solid-liquid separation to obtain a solid. The resulting solid is washed with an aqueous solution containing an organic ligand, and the operation of solid-liquid separation is performed at least once, preferably at least twice. The resulting solid may also be dried so that the moisture content falls within the above-mentioned specific range, and pulverized as necessary.

The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Also, it is preferably a saturated concentration or less.
The concentration of the aqueous solution of the transition metal cyanide compound is preferably from 2 to 50% by mass, more preferably from 2 to 20% by mass, and even more preferably from 3 to 10% by mass.
The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the transition metal cyanide compound is preferably 1.6-12, and more preferably 1.8-8.

The reaction temperature in the reaction between the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

The concentration of the organic ligand in the aqueous solution of the organic ligand is preferably 10 to 90% by mass, more preferably 25 to 75% by mass, and even more preferably 35 to 65% by mass.

The temperature at which the organic ligand is coordinated is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

After the organic ligand is coordinated, it is preferable to perform solid-liquid separation. For solid-liquid separation, methods known in the art, such as filtration and centrifugation, can be used. The obtained solid contains the DMC catalyst as well as salts (alkali metal halides) generated by the reaction. Therefore, it is preferable to remove the salts by washing the obtained solid. Specifically, an aqueous solution of the organic ligand is added to the obtained solid, the mixture is stirred, and then solid-liquid separation is performed again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to perform washing multiple times.

When producing a slurry catalyst, a method can be used in which a mixed liquid containing the DMC catalyst and water is obtained as described above, impurities and water are removed from the resulting mixed liquid, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst and the dispersion medium. Note that washing with an aqueous solution of an organic ligand may be performed before adding the dispersion medium.

<Polymerization of AO>
The initiator and the AO-containing raw material are contacted in the presence of a DMC catalyst, whereby AO in the AO-containing raw material is polymerized (ring-opening addition polymerization) with the initiator.
When a DMC catalyst is used as the polymerization catalyst for AO, the Mw/Mn of the polyether compound tends to be smaller and the degree of unsaturation of the polyether compound tends to be smaller, as compared with the case where a polymerization catalyst other than a DMC catalyst is used.

When the polyoxyalkylene chain of the polyether compound is a random copolymer chain consisting of PO units and EO units, a method of obtaining the polyether compound by contacting an initiator with an AO-containing raw material containing PO and EO in the presence of a DMC catalyst is preferred. The same applies to combinations of two or more AOs other than the combination of PO and EO.

When the polyoxyalkylene chain of the polyether compound is a block copolymer chain having a block of PO units and a block of EO units, an initiator may be reacted with an AO-containing raw material containing PO in the presence of a DMC catalyst to obtain a precursor, and then the precursor may be reacted with an AO-containing raw material containing EO to obtain a polyether compound, or an initiator may be reacted with an AO-containing raw material containing EO in the presence of a DMC catalyst to obtain a precursor, and then the precursor may be reacted with an AO-containing raw material containing PO to obtain a polyether compound. The same applies to combinations of two or more AOs other than the combination of PO and EO.

The amount of DMC catalyst used is preferably 1 to 200 ppm, more preferably 5 to 60 ppm, and particularly preferably 10 to 50 ppm, based on the total mass of the polyether compound finally obtained. If the amount of DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction is likely to proceed. If the amount of DMC catalyst used is equal to or less than the upper limit, the amount of DMC catalyst used is reduced, which is economical.

The polymerization may be carried out in a continuous manner or a batch manner, but is preferably carried out in a batch manner.
The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and even more preferably from 90 to 140°C.
The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less.
The AO-containing raw material is preferably fed to the reactor at a rate that maintains the above reaction temperature.
The reaction atmosphere is preferably one which is less susceptible to moisture contamination, and is more preferably an inert gas atmosphere such as nitrogen.

The reaction liquid after the polymerization contains a polyether compound and a DMC catalyst. It may also contain a stabilizer and may contain trace amounts of impurities. Therefore, it is preferable to purify the reaction liquid by filtration.

<Polyether Compound>
The main chain of the polyether compound is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more kinds of repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer is simply referred to as a "monomer unit", for example, a repeating unit based on AO is referred to as an "AO unit".) In the case of a polymer chain having two or more kinds of AO units, the AO units may form a block polymer or a random polymer.
Examples of the oxyalkylene chain include a polymer chain having an EO unit, a polymer chain having a PO unit, a polymer chain having an EO unit and a PO unit, a polymer chain consisting of an EO unit, a polymer chain consisting of a PO unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an EO unit and a PO unit, and a polymer chain consisting of a PO unit and a butylene oxide unit. As the oxyalkylene chain, a polymer chain consisting of an AO unit having 3 or more carbon atoms is preferred, and a polymer chain consisting of a PO unit is particularly preferred.
The terminal groups of the polyether compound are hydroxyl groups, and the number of terminal groups (i.e., the number of hydroxyl groups) of the polyether compound is the same as the number of active hydrogens of the initiator.

The Mn of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. If the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. If the Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

The hydroxyl value of the polyether compound is preferably 0.5 to 350 mgKOH/g, more preferably 1 to 200 mgKOH/g, and even more preferably 5 to 100 mgKOH/g. If the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when resinified. If the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

The hydroxyl value-equivalent molecular weight of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. If the hydroxyl value-equivalent molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. If the hydroxyl value-equivalent molecular weight is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

The Mw of the polyether compound is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. If the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. If the Mw is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

The Mw/Mn of the polyether compound is preferably 1.00 to 1.15, more preferably 1.00 to 1.12, and even more preferably 1.00 to 1.10. When the Mw/Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

The degree of unsaturation of the polyether compound is preferably 0.001 to 0.040 meq/g, more preferably 0.002 to 0.030 meq/g, and even more preferably 0.003 to 0.010 meq/g.

The content of ultra-high molecular weight components in the polyether compound is preferably less than 2,800 ppm, more preferably 2,700 ppm or less, and even more preferably 2,600 ppm or less, based on the total mass of the polyether compound. When the content of ultra-high molecular weight components is equal to or less than the above upper limit, the physical properties (e.g., stability, strength, etc.) of the article manufactured using the polyether compound are superior.

The viscosity of the polyether compound at a measurement temperature of 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 80,000 mPa·s, and even more preferably 400 to 60,000 mPa·s.

<Applications of polyether compounds>
The polyether compound can be used as a lubricant, a raw material for polyurethane foam, an adhesive, a sealing material, a coating material, etc. In addition, the polyether compound may be reacted with a compound capable of reacting with a hydroxyl group to produce a polyether compound having a reactive silicon group, a prepolymer, or a polyether compound having a polymerizable unsaturated group.

<Polyether Compound Having Reactive Silicon Group>
The polyether compound having a reactive silicon group (hereinafter also referred to as "polyether compound A") has a reactive silicon group represented by formula 2 described below.

(Reactive Silicon Group)
The reactive silicon group has a hydroxyl group, a halogen atom, or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond to crosslink. The reaction to form the siloxane bond is accelerated by a curing catalyst. The reactive silicon group in the polyether compound A is represented by the following formula 2.
-SiR _a X _3-a formula 2

In the above formula 2, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group.
R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

R is preferably at least one group 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 group 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. A methyl group or an ethyl group is preferred in terms of the good curability of the polyether compound A and the stability of the curable composition. An α-chloromethyl group is preferred in terms of the fast curing rate of the cured product. A methyl group is particularly preferred in terms of ease of availability.

In the above formula 2, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group.
Examples of the hydrolyzable group include 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.
An alkoxy group is preferred because it is 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, it is easy to form a siloxane bond quickly and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

In the above formula 2, a is an integer of 0 to 2. When a is 2, the Rs may be the same or different. When a is 1 or less, the Xs may be the same or different. If the crosslinking density due to the siloxane bond decreases, the modulus of the cured product tends to decrease, so a is preferably 2 or less, and more preferably 1 or less.

Examples of reactive silicon groups represented by the above formula 2 include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, methyldiisopropoxysilyl, (α-chloromethyl)dimethoxysilyl, and (α-chloromethyl)diethoxysilyl. In terms of high activity and good curing properties, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl groups are preferred, with dimethoxymethylsilyl being more preferred.

Polyether compound A is a polyether compound having an average of 1.0 or more terminal groups per molecule, a reactive silicon group represented by the above formula 1, and the above terminal group is a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

Polyether compound A has an average of 1.0 or more terminal groups per molecule. The average number of terminal groups is preferably 1.0 to 8.0, more preferably 2.0 to 6.0, and even more preferably 2.0 to 4.0, since the cured product has a higher tensile strength and better modulus and elongation. The number of terminal groups of polyether compound A is the same as the number of terminal groups of the above polyether compound. The terminal groups of polyether compound A have any of the reactive silicon groups, unsaturated groups, isocyanate groups, or hydroxyl groups represented by the above formula 2. The respective terminal groups may be the same or different from each other.

The average number of reactive silicon groups represented by the above formula 2 per terminal group of polyether compound A is preferably 0.5 to 2.0, more preferably 0.60 to 1.94. If the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds will be high, and a good cured product with a high modulus can be obtained.

The average number of reactive silicon groups represented by the above formula 2 per molecule of polyether compound A is preferably 0.6 to 8.0, more preferably 0.8 to 6.0, and even more preferably 1.2 to 4.0. If the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds will be high, and a good cured product with a high modulus can be obtained.

The Mn of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and particularly preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When Mn is equal to or less than the upper limit, the viscosity is low and workability is good.

The Mw/Mn of polyether compound A is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, even more preferably 1.00 to 1.40, and most preferably 1.00 to 1.20. When Mw/Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

The viscosity of polyether compound A at a measurement temperature of 25°C is preferably 100 to 120,000 mPa·s, more preferably 200 to 100,000 mPa·s, and even more preferably 400 to 80,000 mPa/s. If the viscosity is equal to or less than the upper limit, handling is excellent.

<Method for producing polyether compound having reactive silicon group>
In the method for producing the polyether compound A, the hydroxyl groups of the polyether compound are converted into groups having a reactive silicon group.
The method for producing the polyether compound A includes the following production methods (a1), (b1) and (c1).
Method (a1): A method in which hydroxyl groups of a polyether compound are converted to alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then the alkenyloxy groups or alkynyloxy groups are reacted with a silylating agent capable of introducing a reactive silicon group, -SiR _a X _3-a, represented by the above formula 2, into the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group, thereby converting the alkenyloxy groups or alkynyloxy groups into a group having the reactive silicon group represented by the above formula 2.
Method (b1): A method of reacting a hydroxyl group of a polyether compound with a silylating agent having a functional group reactive with the hydroxyl group and a reactive silicon group represented by the above formula 2, thereby converting the hydroxyl group into a group having the reactive silicon group represented by the above formula 2.
Method (c1): A method in which a hydroxyl group of a polyether compound is converted to a group having an isocyanate group, and then a silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted to convert the hydroxyl group to a group having a reactive silicon group represented by the above formula 2.

In method (a1), polyether compound A is subjected to the action of an alkali metal salt to form an alcoholate, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular end or a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular end to convert the hydroxyl groups of the polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular end or alkynyloxy groups having a carbon-carbon triple bond at the molecular end.

Examples of the alkali metal salt include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
From the viewpoints 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 particularly preferred.
The alkali metal salt may be used in a state dissolved in a solvent.

Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminal include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred.
Examples of halogenated hydrocarbon compounds containing a carbon-carbon triple bond at the molecular end 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-butyne, Examples of the iodine include 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, and 6-iodo-1-hexyne. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred.
A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal and a halogenated hydrocarbon compound having a triple bond at the molecular terminal may be used in combination. The halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal may be used alone or in combination of two or more. The halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal may be used alone or in combination of two or more.

Next, a silylating agent capable of introducing a reactive silicon group -SiR _a X _3-a represented by the above formula 2 is reacted with the carbon-carbon double bond at the molecular end of the alkenyloxy group or the carbon-carbon triple bond at the molecular end of the alkynyloxy group to convert the alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by the above formula 2. Examples of the silylating agent 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 represented by the above formula 2, and hydrosilane compounds (e.g., HSiR _a X _3-a , where R, X, and a are the same as those in formula 2). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. In terms of high activity and good curing properties, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

In the method (b1), a polyether compound is reacted with a silylating agent. As the silylating agent, an isocyanate silane compound represented by the following formula 3 is preferably used.
OCN-(CH ₂ ) _n -SiR _a X _3-a ...Formula 3
In the above formula 3, —SiR _a X _3-a is the same as in the above formula 2. n is an integer of 1 to 8, and preferably 1 to 3.
By the reaction between the hydroxyl group of the polyether compound and the isocyanate silane compound, the hydroxyl group of the polyether compound is converted to a terminal group having a urethane bond (--O--C(=O)NH--) and -SiR _a X _3-a , represented by --O--C(=O)NH--(CH ₂ ) _n -SiR _a X _3-a .
Examples of the isocyanate silane compound include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl methyl diethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl methyl diethoxy silane.
As the isocyanate silane compound, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, isocyanate methyl methyl dimethoxy silane and isocyanate methyl trimethoxy silane are preferred from the viewpoints of reactivity with polyether compounds and ease of handling.

The active hydrogen of the polyether compound reacts with the isocyanate group of the isocyanate silane compound represented by the above formula 3, whereby a reactive silicon group is introduced into the polyether compound.
When the active hydrogen-containing group of the polyether compound is a hydroxyl group, a polyether compound A is obtained in which a reactive silicon group is bonded to a polyoxyalkylene chain (-(R ⁵ O) _m -, where R ⁵ represents an alkylene group and m represents the number of moles of oxyalkylene groups) via a urethane bond and an organic group. That is, a linking structure represented by -(R ⁵ O) _m -C(=O)NH-(CH ₂ ) _n -SiR _a X _3-a is formed.

This reaction may be carried out in the presence of a urethanization catalyst. The urethanization catalyst is not particularly limited, and any known urethanization catalyst can be used as appropriate. Examples include organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, and more preferably 50 to 150°C. The urethanization reaction is preferably carried out in an inert gas atmosphere. Nitrogen is a preferred inert gas.

The molar ratio of the total number of isocyanate groups of the isocyanate silane compound represented by formula 3 to the total number of active hydrogens of the polyether compound is preferably set according to the number of reactive silicon groups per molecule of the polyether compound A to be obtained. It is preferable to react the isocyanate silane compound represented by formula 3 above so that the number of reactive silicon groups per molecule of the obtained polyether compound A is at least 0.7.
For example, when the active hydrogen-containing group of the polyether compound is a hydroxyl group, NCO/OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3 to the total number of active hydrogens (total number of hydroxyl groups) of the polyether compound, is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and even more preferably 0.9 to 1.0. When NCO/OH is equal to or greater than the lower limit, the strength of the cured product is excellent, and when it is equal to or less than the upper limit, the elongation of the cured product is excellent.

In method (c1), a polyisocyanate compound is reacted with a hydroxyl group of a polyether compound to convert the hydroxyl group into a monovalent organic group containing an isocyanate group (hereinafter also referred to as an "isocyanate-containing group") having a urethane bond (-O-C(=O)NH-) at the bond terminal side with the polyether compound, and then a silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted with the isocyanate-containing group to form an end group which is a monovalent organic group (hereinafter also referred to as a "urethane bond-and-reactive silicon group-containing group") having one or more urethane bonds (-O-C(=O)NH-) and a silylating agent residue reacted with an isocyanate group.
Hereinafter, method (c1) will be described assuming that the polyisocyanate compound is a diisocyanate compound represented by the following formula 4, and that the silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is a compound represented by the following formula 5, but the present invention is not limited thereto.

OCN-R ³ -NCO...Formula 4
In the above formula 4, ^R3 represents a divalent organic group.

WR ⁴ -SiR _a X _3-a ...Formula 5
In the above formula 5, W is a functional group capable of reacting with a monovalent isocyanate group (a group having one or more active hydrogens), R ⁴ is a divalent organic group, -SiR _a X _3-a is a group represented by the above formula. Same as 2.

When the hydroxyl group of a polyether compound is reacted with a diisocyanate compound represented by the above formula 4, the isocyanate-containing group is a group represented by -O-C(=O)NH-R ³ -NCO. When the isocyanate-containing group is reacted with a silylating agent represented by the above formula 5, the urethane bond and reactive silicon group-containing group are a group represented by -O-C(=O)NH-R ³ -NHC(=O)-W'-R ⁴ -SiR _a X _3-a (wherein W' is a divalent group obtained by removing one active hydrogen from W). For example, when W is a hydroxyl group, the urethane bond and reactive silicon group-containing group are a group represented by -O-C(=O)NH-R ³ -NHC(=O)-O-R ⁴ -SiR _a X _3-a . In this case, the urethane bond and reactive silicon group-containing group have two urethane bonds. Furthermore, for example, when W is an amino group (-NH ₂ ), the urethane bond and reactive silicon group-containing group are groups represented by -O-C(=O)NH-R ³ -NHC(=O)-NH-R ⁴ -SiR _a X _3-a .

^R3 is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which may have an alkyl group as a substituent and are bonded via an alkylene group, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group as a substituent and are bonded via an alkylene group.

Examples of the diisocyanate compound represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanates and alicyclic polyisocyanates, as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.
Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylenepolymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.
Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate).
The polyisocyanate compound is preferably one having two isocyanate groups, more preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, and even more preferably tolylene diisocyanate because it is easy to obtain a tensile strength of the cured product. The polyisocyanate compound may be used alone or in combination of two or more kinds.

R ⁴ in the silylating agent having a functional group reactive with an isocyanate group represented by formula 5 and -SiR _a X _3-a is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms and having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms, still more preferably a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms, and particularly preferably a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms.
W is preferably a group having one or two active hydrogens selected from a hydroxyl group, a carboxyl group, a sulfanyl group, an amino group, and an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms, more preferably a hydroxyl group, a sulfanyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group, and more preferably a hydroxyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group.

In the case of the methods (b1) and (c1), the polyether compound A obtained has a reactive silicon group formed via one or more organic groups represented by the following formula (i). That is, the polyether compound A obtained by the methods (b1) and (c1) contains one or more organic groups represented by the following formula (i). Note that the polyether compound A obtained by the method (b1) contains only one organic group represented by the following formula (i), and the polyether compound A obtained by the method (c1) contains two or more organic groups represented by the following formula (i).
-C(=O)NH- Formula (i)

The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by the above formula 3 is used as a silylating agent, there is one organic group (i).

It is preferable that the organic group (i) forms a urethane bond (-O-C(=O)NH-, -O- represents the oxygen atom at the end of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) is present between the polyoxyalkylene chain and the reactive silicon group in the polyether compound A. When the polyether compound A is produced by the above-mentioned method (b1), the number of organic groups represented by the above formula (i) contained in the polyether compound A is one. When the polyether compound A is produced by the method (b1), a polyether compound A having a high silylation rate is easily obtained. When the polyether compound A is produced by the method (b1), a polyether compound A having a narrow molecular weight distribution is easily obtained. Since the viscosity of the polyether compound is suppressed, the workability is improved.
When the isocyanate silane compound represented by the above formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polyether compound A is the same as the number of groups (i) per molecule.

The silylation rate of the polyether compound A is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is equal to or higher than the lower limit of the above range, the cured product has excellent tensile strength and a high modulus.
When the curable composition contains two or more types of polyether compounds A, it is sufficient that the average silylation rate of all the polyether compounds A is within the above range.

(Curable composition containing polyether compound having reactive silicon group)
The polyether compound A is used in a curable composition. The curable composition is obtained by mixing the polyether compound A with other necessary components. As the polyether compound A, only one type may be used, or two or more types may be used in combination.
The content of the polyether compound having a reactive silicon group relative to the total mass of the curable composition is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%. When it is equal to or less than the upper limit of the above range, the cured product has better tensile strength and elongation properties.

Examples of other components contained in the curable composition include curable compounds other than polyether compound A, such as epoxy resins, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropy-imparting agents, stabilizers, adhesion-imparting agents, physical property adjusters, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates.
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.

The curable composition may be a one-component type in which the polyether compound A and all other components are mixed in advance, stored in a sealed state, and cured by moisture in the air after application, or a two-component type in which a base composition containing at least the polyether compound A and a hardener composition containing at least a curing catalyst are stored separately, and the hardener composition and the base composition are mixed before use.
It is preferable that the one-liquid type curable composition does not contain water. It is preferable that the blended components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during blending and kneading.
In the two-part curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of moisture, but from the viewpoint of storage stability, it is preferable to previously dehydrate and dry the blended components.
In order to improve storage stability, a dehydrating agent may be added to the one-part curable composition or the two-part base composition.

(Uses of the curable composition containing a polyether compound having a reactive silicon group)
Suitable applications of the curable composition containing polyether compound A include adhesives, sealants (e.g., elastic sealants for architecture, sealants for insulating glass, anti-rust and waterproof sealants for glass ends, sealants for the rear surface of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), and electrical insulating materials (insulating coating materials for electric wires and cables).

<Prepolymer>
The prepolymer (hereinafter also referred to as "polyether compound B") is a reaction product of a polyether compound and a polyisocyanate. A urethane bond is formed between the polyether compound and the polyisocyanate by a urethane reaction between the hydroxyl group of the polyether compound and the isocyanate group of the polyisocyanate. Among the isocyanate groups in the polyisocyanate unit introduced into the polyether compound B, the isocyanate group remaining unreacted with the hydroxyl group of the polyether compound B becomes the isocyanate group at the molecular end of the polyether compound B. In addition, among the hydroxyl groups in the polyether compound unit, the hydroxyl group remaining unreacted with the isocyanate group of the polyisocyanate becomes the hydroxyl group at the molecular end of the polyether compound B. That is, the molecular end group of the polyether compound B contains either one or both of a hydroxyl group and an isocyanate group.

The Mn of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are obtained when used as an adhesive or coating material. When Mn is equal to or less than the upper limit, the viscosity of polyether compound B can be kept low, making it easy to handle.

The Mw/Mn of polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When Mw/Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

When the molecular terminal of polyether compound B is an isocyanate group, the content of the isocyanate group relative to the total mass of polyether compound B is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, and further preferably 1 to 15 mass%.
When the content of isocyanate groups is equal to or greater than the above lower limit, the tensile strength of the cured product is likely to be improved.When the content of isocyanate groups is equal to or less than the above upper limit, gelation is unlikely to occur during the reaction.

The content of urethane bonds relative to the total mass of polyether compound B is preferably 0.01 to 40 mass%, more preferably 0.1 to 30 mass%, and even more preferably 1 to 15 mass%.

The viscosity of polyether compound B at a measurement temperature of 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa/s. If the viscosity is equal to or less than the upper limit, handling is excellent.

<Production method of prepolymer>
In the method for producing the polyether compound B, a polyether compound is reacted with a polyisocyanate. If necessary, a urethane catalyst may be used. The polyether compound may be used alone or in combination of two or more kinds.

Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The number of isocyanate groups contained in the polyisocyanate is preferably 2 to 3, and more preferably 2.

Examples of aliphatic polyisocyanates include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, as well as branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

Examples of aromatic polyisocyanates include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (diphenylmethane 4,4'-diisocyanate, MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

Examples of aromatic aliphatic polyisocyanates include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI, MDI and TDI are more preferred.
One type of polyisocyanate may be used alone, or two or more types may be used in combination.

The functional groups at the molecular ends of polyether compound B can be controlled by adjusting the molar ratio of the total amount of isocyanate groups in the polyisocyanate to the total amount of hydroxyl groups in the polyether compound (hereinafter also referred to as the "NCO/OH ratio"). For example, when producing polyether compound B whose molecular ends are isocyanate groups, the NCO/OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing polyether compound B whose molecular ends are hydroxyl groups, the NCO/OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

As the urethane catalyst, one or more selected from tertiary amine compounds and organometallic compounds are preferred. When a highly reactive polyisocyanate is used, it is not necessary to use a urethane catalyst.

Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

The organometallic compound is preferably at least one selected from tin-based compounds and non-tin-based compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium trichloride, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

The urethanization catalyst may be used alone or in combination of two or more kinds.
When a urethanization catalyst is used, the amount of the urethanization catalyst used is preferably, for example, 0.001 to 1.0 part by mass per 100 parts by mass of the polyether compound.

In the production of the polyether compound B, a solvent can be used, if necessary.
The solvent is preferably one or more selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene.
The solvent may be used alone or in combination of two or more kinds.
When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1,000 parts by mass per 100 parts by mass of the polyether compound.

The method for producing polyether compound B may, for example, be a method of mixing a polyether compound, a polyisocyanate, and, if necessary, a urethane-forming catalyst and a solvent. Alternatively, a method may be used in which polyisocyanate is added dropwise to a mixed liquid obtained by mixing a polyether compound, and, if necessary, a urethane-forming catalyst and a solvent.

The reaction temperature is preferably 50 to 120°C, more preferably 50 to 100°C. If the reaction temperature is equal to or higher than the lower limit, the urethane reaction is likely to be accelerated. If the reaction temperature is equal to or lower than the upper limit, side reactions other than the urethane reaction are likely to be suppressed.

When a urethanization catalyst is used, it is preferable to inactivate the urethanization catalyst after the completion of the reaction by adding a reaction terminator such as acetylacetone.
The reaction terminator may be used alone or in combination of two or more kinds.

If unreacted polyisocyanate remains after the reaction, it is preferable to remove the polyisocyanate by distillation and purify polyether compound B.

(Polyurethane Composition Containing Prepolymer)
The polyether compound B is used in a polyurethane composition. The polyurethane composition is obtained by mixing the polyether compound B with other optional components as necessary. As the polyether compound B, only one type may be used, or two or more types may be used in combination.
The content ratio of polyether compound B to the total mass of the polyurethane composition is 15 mass % or more and 100 mass % or less, and preferably 30 to 100 mass %. The polyurethane composition may further contain optional components other than polyether compound B.

Optional components contained in the polyurethane composition include catalysts, fillers, plasticizers, stabilizers, pigments, fibers, dyes, drying agents, adhesion improvers, rheology modifiers, solvents, natural resins, non-reactive polymers, and other additives. Each of the optional components may be used alone or in combination of two or more. When the polyurethane composition contains optional components, the content of the optional components relative to the total mass of the polyurethane composition is preferably more than 0 mass% and not more than 50 mass%.

A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular end of the polyether compound B is an isocyanate group, a curing agent having active hydrogen is used. The active hydrogen-containing group of the curing agent is preferably a hydroxyl group. When the molecular end of the polyether compound B is a hydroxyl group, a curing agent having an isocyanate group is used.
When the molecular end of polyether compound B is an isocyanate group, the isocyanate group of polyether compound B contained in the polyurethane composition and the active hydrogen-containing group (e.g., hydroxyl group) of the curing agent undergo a urethane reaction to crosslink polyether compound B with a urethane bond, thereby obtaining a cured product. When the molecular end of polyether compound B is a hydroxyl group, the hydroxyl group of polyether compound B contained in the polyurethane composition and the isocyanate group of the curing agent undergo a urethane reaction to crosslink polyether compound B with a urethane bond, thereby obtaining a cured product.
In the case of a curing agent having a hydroxyl group, the number of hydroxyl groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3. Note that water is a curing agent having two hydroxyl groups.
In the case of a curing agent having an isocyanate group, the number of isocyanate groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3.

Examples of the curing agent having a hydroxyl group include the initiators and water described in the method for producing the polyether compound.
The curing agent having an isocyanate group is exemplified by the above-mentioned polyisocyanates.

When the molecular terminal of polyether compound B is an isocyanate group, the molar ratio of the total amount of isocyanate groups of polyether compound B to the total amount of hydroxyl groups of the curing agent is preferably more than 1, more preferably 1.0 to 1.2.
When the molecular terminal of polyether compound B is a hydroxyl group, the molar ratio of the total amount of hydroxyl groups of polyether compound B to the total amount of isocyanate groups of the curing agent is preferably more than 0.8, more preferably 0.8 to 1.2.

The method of mixing the polyurethane composition and the curing agent may be a one-component type in which the polyurethane composition, which is a one-component composition obtained by previously mixing everything except the curing agent, is sealed and stored, and then cured by moisture in the air after application, or a two-component type in which the polyurethane composition, which is the base composition, and the curing agent composition containing at least the curing agent are stored separately, and the curing agent composition and the base composition are mixed before use. In the case of the one-component type, moisture (water) in the air functions as the curing agent. That is, when the molecular end of the polyether compound B is an isocyanate group, the one-component type is preferred.
The one-liquid composition preferably does not contain water. It is preferable that the components containing water are dehydrated and dried in advance, or that they are dehydrated under reduced pressure during the preparation of the one-liquid composition.
In the case of the two-liquid type, the hardener 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 to dehydrate and dry the blended components in advance. In the case of the two-liquid type, the above-mentioned optional components may be included in the hardener composition.
In order to improve storage stability, a dehydrating agent may be added to the one-liquid composition or the two-liquid base composition.
The reaction temperature is preferably 20 to 40° C. In the case of a one-liquid type, the relative humidity at the above reaction temperature is preferably 40 to 60%.

(Uses of polyurethane compositions containing prepolymers)
Suitable applications of the polyurethane composition containing a prepolymer include adhesives, sealants (e.g., elastic sealants for architecture, sealants for insulating glass, anti-rust and waterproof sealants for glass ends, sealants for the rear surfaces of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), coating materials (for paint applications), and electrical insulating materials (insulating coating materials for electric wires and cables).
As an adhesive, it is suitable as an elastic adhesive for joining plastics together, metals together, and plastics and metals, and is also suitable as an elastic sealing material and elastic coating material.

<Polyether Compound Having Polymerizable Unsaturated Group>
A polyether compound having a polymerizable unsaturated group (hereinafter also referred to as "polyether compound C") is a reaction product of a polyether compound and a compound having a polymerizable unsaturated group. An example of the polymerizable unsaturated group is a carbon-carbon double bond at a molecular terminal. Preferred polymerizable unsaturated groups are a (meth)acryloyl group and a (meth)acryloyloxy group. "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. "(meth)acryloyloxy group" is a general term for an acryloyloxy group and a methacryloyloxy group.

Polyether compound C has an average of 1.0 or more terminal groups per molecule. Since this improves the crosslinking reaction and curing properties when resinified, the average number of terminal groups is preferably 1.0 to 8.0, more preferably 2.0 to 6.0, and even more preferably 2.0 to 4.0. The number of terminal groups of polyether compound C is the same as the number of terminal groups of the above polyether compound.

The average number of polymerizable unsaturated groups per terminal group of the polyether compound C is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2. If the average number of polymerizable unsaturated groups is equal to or greater than the above lower limit, the crosslinking reaction and curing properties when resinified tend to be good. If the average number of polymerizable unsaturated groups is equal to or less than the above upper limit, the resin is given sufficient flexibility, and good elongation properties tend to be obtained.

The average number of polymerizable unsaturated groups per molecule of polyether compound C is preferably 1.0 to 8.0, more preferably 1.5 to 6.0, and even more preferably 2.0 to 4.0. If the average number of polymerizable unsaturated groups is equal to or greater than the above lower limit, the crosslinking reaction and curing properties when resinified tend to be good. If the average number of polymerizable unsaturated groups is equal to or less than the above upper limit, the resin is given sufficient flexibility, and good elongation properties tend to be obtained.

The Mn of polyether compound C is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are easily obtained. When Mn is equal to or less than the upper limit, the viscosity of polyether compound C can be kept low, making it easy to handle.

The Mw/Mn of polyether compound C is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When Mw/Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, improving workability.

When polyether compound C has a urethane bond, the content of the urethane bond relative to the total mass of polyether compound C is preferably 0.01 to 40 mass%, more preferably 0.1 to 30 mass%, and even more preferably 1 to 15 mass%.

The viscosity of polyether compound C at a measurement temperature of 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa/s. If the viscosity is equal to or less than the upper limit above, handling is excellent.

<Method of producing polyether compound having polymerizable unsaturated group>
In the method for producing the polyether compound C, a hydroxyl group of the polyether compound is converted into a group having a polymerizable unsaturated group.
The method for producing the polyether compound C may be the following method (a2), (b2) or (c2).
Method (a2): A method in which a compound having a functional group reactive with the hydroxyl group of a polyether compound and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") is reacted with the hydroxyl group to convert the hydroxyl group into a group having a polymerizable unsaturated group.
Method (b2): A method in which a hydroxyl group of a polyether compound is reacted with a polyisocyanate to obtain a prepolymer having an isocyanate group at the molecular end, and then a compound having a functional group reactive with an isocyanate group and a polymerizable unsaturated group (hereinafter also referred to as "compound 2") is reacted to convert the hydroxyl group into a group having a polymerizable unsaturated group.
Method (c2): A method in which a hydroxyl group of a polyether compound is reacted with a polyisocyanate to obtain a prepolymer having a hydroxyl group at the molecular end, and then the prepolymer is reacted with the above-mentioned compound 1 to convert the hydroxyl group into a group having a polymerizable unsaturated group.

As the prepolymer having an isocyanate group at the molecular end in method (b2), the above-mentioned polyether compound B having an isocyanate group at the molecular end can be used. As the prepolymer having a hydroxyl group at the molecular end in method (c2), the above-mentioned polyether compound B having a hydroxyl group at the molecular end can be used.

Compound 1 is preferably a compound having one isocyanate group and a polymerizable unsaturated group, more preferably a (meth)acrylate having one isocyanate group, even more preferably an isocyanate alkyl (meth)acrylate, particularly preferably an isocyanate alkyl (meth)acrylate having 8 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group, and most preferably an isocyanate alkyl (meth)acrylate having 4 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group. "(Meth)acrylate" is a general term for acrylate and methacrylate.
Examples of compound 2 include 2-isocyanate ethyl (meth)acrylate, isocyanate methyl (meth)acrylate, etc. Commercially available products include Karenz-AOI and Karenz-MOI (both are product names of Showa Denko KK).

As compound 2, a compound having an active hydrogen-containing group such as a hydroxyl group or an amino group, and a polymerizable unsaturated group is preferable, a (meth)acrylate having an active hydrogen-containing group such as a hydroxyl group or an amino group is preferable, a hydroxyalkyl (meth)acrylate or a hydroxycycloalkyl (meth)acrylate having one hydroxyl group is more preferable, and a hydroxyalkyl (meth)acrylate having an alkyl group with 8 or less carbon atoms is particularly preferable.
Examples of compound 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. Commercially available products include Light Ester HO-250(N), Light Ester HOP(N), Light Ester HOA(N), Light Ester HOP-A(N), Light Ester HOB(N) (all of which are Kyoei Chemical Co., Ltd. product names), and 4-HBA (Osaka Organic Chemical Industry Co., Ltd. product name).

When the composition containing polyether compound C is a photocurable composition, it is preferable that all of the polymerizable unsaturated groups contained in polyether compound C are acryloyloxy groups. Such a polyether compound C can be obtained by using compounds 1 and 2 in which the polymerizable unsaturated groups are acryloyloxy groups.

In the methods (a2) and (c2), the molar ratio of the amount of compound 1 used relative to the amount of hydroxyl groups in the polyether compound or the amount of hydroxyl groups in the prepolymer having hydroxyl groups at the molecular terminals is preferably from 0.8 to 1.2, more preferably from 0.9 to 1.1, and even more preferably from 0.95 to 1.05.
In the method (b2), the molar ratio of the amount of compound 2 used relative to the amount of isocyanate groups in the prepolymer having an isocyanate group at the molecular terminal may be more than 1. Excess compound 2 remains unreacted, but may be contained in the composition containing polyether compound C. The molar ratio is preferably 0.8 to 1.5, more preferably 0.9 to 1.3, and even more preferably 0.95 to 1.1.

In the methods (a2), (b2) and (c2), the reaction between a hydroxyl group and a functional group capable of reacting with the hydroxyl group, and the reaction between an isocyanate group and a functional group capable of reacting with the isocyanate group can be carried out by a method known in the art. When the reaction is between a hydroxyl group and an isocyanate group, the above-mentioned urethane catalyst may be used as necessary.

(Composition containing a polyether compound having a polymerizable unsaturated group)
The polyether compound C is used in a curable composition. The curable composition is obtained by mixing the polyether compound C with other optional components. As the polyether compound C, only one type may be used, or two or more types may be used in combination.
The content of the polyether compound C relative to the total mass of the curable composition is preferably 65 mass % or more, and more preferably 75 mass % or more.

In addition to polyether compound C, the curable composition may contain a compound having a polymerizable unsaturated group other than polyether compound C (hereinafter also referred to as "other compound"), a photopolymerization initiator, and other components.

Examples of the other compounds include the following other compounds 1 and 2.
The other compound 1 is a compound other than the polyether compound C, and is preferably a compound having one (meth)acryloyloxy group and one or more hydroxyl groups, and preferably has one or two hydroxyl groups. The other compound 1 may be a compound having a polyoxyalkylene chain, and in this case, a compound having no urethane bond or urea bond (a compound produced by a method other than the above methods (a2) to (c2)) is preferred. The other compound may be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of lactone.

Other examples of compound 1 include hydroxyalkyl (meth)acrylates, dihydroxyalkyl (meth)acrylates, lactone-modified hydroxyalkyl (meth)acrylates, polyoxyalkylene diol mono(meth)acrylates, (meth)acrylic acid-monoepoxide adducts, etc.

The number of carbon atoms in the hydroxyalkyl portion of the hydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl portion of the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. Specific examples of hydroxyalkyl (meth)acrylates include the hydroxyalkyl (meth)acrylates exemplified as compound 2 above. Among these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactones to the hydroxyalkyl (meth)acrylates exemplified as compound 2 above. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

Preferred examples of the (meth)acrylic acid-monoepoxide adduct include reaction products of (meth)acrylic acid with glycidyl ether or glycidyl ester, such as (meth)acrylic acid and phenyl glycidyl ether.

Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain fewer impurities.

The other compounds 1 may be used alone or in combination of two or more.
When the curable composition contains the other compound 1, the content of the other compound 1 relative to the total mass of the curable composition is preferably 1 to 20 mass%, more preferably 1 to 15 mass%. When the content of the other compound 1 is equal to or more than the above lower limit, the effect of improving adhesion by adding the other compound 1 is easily obtained. When the content of the other compound 1 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are easily obtained.

The other compound 2 is a compound other than the polyether compound C and the other compound 1, and is preferably a compound having one (meth)acryloyloxy group and not containing a urethane bond.
Preferred examples of the other compound 2 include a (meth)acrylate having a long-chain alkyl group having 8 or more carbon atoms and a (meth)acrylate having an amide group. Examples of the other compound 2 other than these include an alkyl (meth)acrylate having 7 or less carbon atoms, an alkoxyalkyl (meth)acrylate, and a (meth)acrylate having an aliphatic cyclic hydrocarbon group.

When the curable composition contains a long-chain alkyl (meth)acrylate having 8 or more carbon atoms, air bubbles in the cured product tend to disappear when the curable composition is sealed under reduced pressure and cured in a higher pressure atmosphere (reduced pressure sealing-pressure increase curing method). The number of carbon atoms in the long-chain alkyl group is preferably 8 to 22, and more preferably 8 to 18.
Examples of long-chain alkyl (meth)acrylates include lauryl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, etc. Among these, lauryl acrylate and isostearyl acrylate are preferred in terms of flexibility, low viscosity, and low crystallinity.

As the (meth)acrylate having an amide group, a compound in which the hydrogen atom bonded to the nitrogen atom of (meth)acrylamide is substituted with a hydrocarbon group such as an alkyl group or a divalent organic group is preferred, since this makes it easier to suppress whitening of the cured product of the curable composition under moist and heat conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

The other compounds 2 may be used alone or in combination of two or more.
When the curable composition contains the other compound 2, the content of the other compound 2 relative to the total mass of the curable composition is preferably 1 to 30 mass%, more preferably 1 to 25 mass%. When the content of the other compound 2 is equal to or more than the above lower limit, the effect of adding the other compound 2 is easily obtained. When the content of the other compound 2 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are easily obtained.

The curable composition may be a photocurable composition or a thermosetting composition. Photocurable compositions are preferred because they can be cured at low temperatures and have a fast curing rate. When the curable composition is a photocurable composition, it preferably contains a photopolymerization initiator. When a photocurable composition is used in the manufacture of a display device, for example, high temperatures are not required, so there is little risk of damage to the display device due to high temperatures.

Examples of photopolymerization initiators include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Of these, phosphine oxide-based and thioxanthone-based photopolymerization initiators are preferred, with phosphine oxide-based being preferred in that coloring after the photopolymerization reaction is easily suppressed. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The photopolymerization initiator is not particularly limited, and commercially available products can be used. Examples of commercially available products include IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02, all of which are manufactured by BASF Corporation.
When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the curable components.

Examples of other components include tackifiers such as rosin esters, terpene phenols, and hydrogenated terpene phenols, plasticizers such as adipates and phthalates, polyether compounds that do not have polymerizable unsaturated groups, and polyether polyols with alkoxylated molecular ends. When the curable composition contains a plasticizer, flexibility and adhesion tend to improve. The content of these compounds relative to the total mass of the curable composition is preferably 48% by mass or less, and more preferably 28% by mass or less.

Other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (UV absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion improvers (silane coupling agents, etc.), pigments, dyes, etc. Among these, it is preferable to include a polymerization inhibitor and a light stabilizer. In particular, by including a smaller amount of polymerization inhibitor than the polymerization initiator, the storage stability of the curable composition can be improved and the molecular weight after curing can be easily adjusted.

Examples of polymerization inhibitors include hydroquinone-based (2,5-di-tert-butylhydroquinone, etc.), catechol-based (p-tert-butylcatechol, etc.), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

The ultraviolet absorber is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of ultraviolet absorbers include benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers. Benzotriazole-based ultraviolet absorbers can be, for example, those described in paragraph [0076] of WO 2014/017328.

The light stabilizer is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of light stabilizers include hindered amine light stabilizers. As the hindered amine light stabilizer, those described in paragraph [0077] of WO 2014/017328 can be used.

The antioxidant is used to prevent oxidation of the curable composition and improve weather resistance and heat resistance. Examples of the antioxidant include phenol-based and phosphorus-based antioxidants. As the phenol-based antioxidant, for example, those described in paragraph [0078] of WO 2014/017328 can be used. As the phosphorus-based antioxidant, those described in paragraph [0078] of WO 2014/017328 can be used.

You can also use products that contain multiple antioxidants, light stabilizers, etc., such as IRGASTAB PUR68 and TINUVIN B75 manufactured by BASF.

When the curable composition contains other components, the total content of the other components is preferably 100 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the curable component.

The amount of chain transfer agent in the curable composition is preferably small, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the curable component, and particularly preferably no chain transfer agent is contained.

(Uses of the curable composition containing the polyether compound having a polymerizable unsaturated group)
Suitable applications of the curable composition containing polyether compound C include pressure sensitive adhesives in the fields of various building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, liquid crystal panels, and the like.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. Examples 1 to 4 are examples, and Examples 5 to 8 are comparative examples.

[Methanol content and AO content of AO-containing raw material]
The methanol content (ppm) and AO content (mass%) relative to the total mass of the AO-containing raw material were measured using a gas chromatograph (detector: flame ionization detector (FID)) under the following conditions.
Column: Capillary, 60 m x 0.32 mm φ, DB-1301 ms, film thickness 1.0 μm
Oven temperature: 35°C (12 min) → 10°C/min → 100°C (12 min)
INJ/DET temperature: 180/180℃
Carrier gas: He
Air flow rate: 400mL/min
_H2 flow rate: 30mL/min
Carrier flow rate (pressure): 1.3609 mL/min (24.056 psi)
Septum purge flow rate: 5 mL/min
Split ratio: 50:1
Split flow rate: 68.047 mL/min
Total flow: 74.407 mL/min
Gas saver: 20mL/min
Injection port: back Injection method: microsyringe, injection amount 2 μL

[Hydroxyl value and hydroxyl value-based molecular weight]
The hydroxyl value (OHV) was calculated in accordance with Method B of JIS K 1557-1:2007. The OHV-equivalent molecular weight was calculated based on the formula "56,100/hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound". The number of hydroxyl groups of the polyether compound is the number of hydroxyl groups of the initiator. When two or more polyether compounds with different numbers of hydroxyl groups are included, the number of hydroxyl groups of the polyether compound is the average number of hydroxyl groups.

[Mn, Mw, Mw/Mn]
The molecular weight of the polyether compound was analyzed using a GPC system (Tosoh Corporation product name HLC-8320) and an RI detector.
The columns used were two TSK-GEL Super HZ4000 (4.6 mm x 150 mm) and two Super HZ2500 (4.6 mm x 150 mm) connected in series in this order. Tetrahydrofuran (THF) was poured at a flow rate of 0. The eluent was 35 ml/min, the column temperature was 40° C., and the conversion was performed based on a calibration curve prepared using a polystyrene standard sample (Agilent Technologies, product name: Easical PS-2, molecular weight range: 580 to 400,000). Mn, Mw and Mw/Mn were determined.

[Ultra-high molecular weight component]
The content of the ultra-high molecular weight component was determined by the CAD-HPLC method. The details of the measurement conditions are as follows.
Apparatus and detector: High performance liquid chromatography apparatus (ThermoFisher SCIENTIFIC product name U3000HPLC system Degasser: SRD-3600, Pump: DGP3600SD, Autosampler: WPS-3000TSL, Column compartment: TCC-3000SD, UV-Vis detector: VWD-3400RS, Charged aerosol detector: Corona Veo)
Eluent: THF for HPLC
Eluent flow rate: 0.2 mL/min Sample injection volume: 20 μL
Columns: One upstream column and one downstream column were connected in series in the following order. The exclusion limit molecular weight of each column is the exclusion limit molecular weight when the molecular weight of polystyrene is measured using HPLC-grade THF as the eluent.
Upstream column: Showa Denko Co., Ltd. product name Shodex KF-404HQ (a column for organic solvent liquid chromatography, with a packing material of styrene-divinylbenzene copolymer with an average particle size of 3 μm, an inner diameter of 4.6 mm, a length of 250 mm, a theoretical plate number of 25,000 or more TP/column, and an exclusion limit molecular weight of 1,000,000)
Downstream column: Showa Denko Co., Ltd. product name Shodex KF-403HQ (a column for organic solvent liquid chromatography, with a packing material of styrene-divinylbenzene copolymer with an average particle size of 3 μm, an inner diameter of 4.6 mm, a length of 250 mm, a theoretical plate number of 25,000 or more TP/column, and an exclusion limit molecular weight of 70,000)

The details of the measurement operations are as follows.
(1) Each polyether compound was dissolved in THF for HPLC to a concentration of 0.6% by mass, and then filtered through a syringe filter having a pore size of 0.45 μm to prepare a sample. The sample was analyzed under the above-mentioned HPLC conditions to obtain a chromatogram in which the retention time is on the X-axis and the signal intensity is on the Y-axis.
(2) A calibration curve showing the relationship between molecular weight and retention time was prepared using a polystyrene standard sample (Agilent Technologies product name: Easical PS-2, molecular weight range: 580 to 400,000).
(3) Using the calibration curve prepared in (2), the retention time X1 corresponding to the above 12 W and the retention time X2 corresponding to the above 46 W were determined.
(4) The area of the portion surrounded by the above chromatogram, the baseline, the line X=X1, and the line X=X2 was calculated by electronic integration.
(5) A standard sample of polystyrene having a molecular weight of 92,600 (Gas Chromatography Co., Ltd. product name PSS-05 No. 500-16) was dissolved in HPLC THF to give a concentration of 1, 6, 20, and 60 ppm, and the standard solution was analyzed under the above HPLC conditions to obtain a chromatogram. The area surrounded by the obtained chromatogram and the baseline was taken as the area. The area at each concentration was calculated, and a calibration curve with an intercept of zero was created, which shows the relationship between the concentration of polystyrene having a molecular weight of 92,600 and the area.
(6) Using the calibration curve prepared in (5), the area determined in (4) was converted into the concentration of polystyrene with a molecular weight of 92,600, which was regarded as the concentration of the ultra-high molecular weight component in the sample prepared in (1).
(7) From the concentration value of the ultra-high molecular weight component obtained in (6), the mass of the ultra-high molecular weight component in the sample prepared in (1) was calculated, and further, the content of the ultra-high molecular weight component relative to the mass of the test substance (polyether compound) used in the preparation of the sample was calculated.

[viscosity]
The viscosity of the polyether compound was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) under conditions of a measurement temperature of 25° C. and rotor No. 1.

[AO-containing raw material]
Eight types of PO (PO (1) to (8)) obtained from different sources and lots were used as the AO-containing raw materials. Table 1 shows the methanol content and AO content of each AO-containing raw material.

[Production Example 1: Preparation of polyol P1 (initiator)]
In the presence of a KOH catalyst, PO(1) was polymerized with propylene glycol, and the resulting mixture was purified by dealkalization to obtain polyoxypropylene diol (hereinafter, also referred to as "polyol P1"). The average number of hydroxyl groups per molecule of polyol P1 was 2, and the molecular weight in terms of OHV was 1,000.

[Production Example 2: Preparation of polyol P2 (initiator)]
In the presence of a KOH catalyst, PO(1) was polymerized with glycerin, and the resulting product was purified by dealkalization to obtain polyoxypropylene triol (hereinafter also referred to as "polyol P2"). The average number of hydroxyl groups per molecule of polyol P2 was 3, and the molecular weight in terms of OHV was 1,000.

[Example 1]
Using polyol P1 as an initiator, PO (1) was polymerized in the presence of a zinc hexacyanocobaltate complex catalyst of tert-butyl alcohol (hereinafter referred to as "TBA-DMC catalyst") until the OHV-equivalent molecular weight reached 12,000, to obtain polyether compound 1. The polymerization was carried out by adding 0.1 mass% of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was an amount such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 1.

[Example 2]
Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, to obtain a polyether compound 2. The polymerization was carried out by adding 0.1 mass% of Irganox 1010 manufactured by BASF as a stabilizer. The amount of the TBA-DMC catalyst used was an amount such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound 2.

[Example 3]
Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, to obtain a polyether compound 3. The polymerization was carried out by adding 0.1 mass% of Irganox 1010 manufactured by BASF as a stabilizer. The amount of the TBA-DMC catalyst used was an amount such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound 3.

[Example 4]
Using polyol P1 as an initiator, PO (4) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, to obtain a polyether compound 4. The polymerization was carried out by adding 0.1 mass% of Irganox 1010 manufactured by BASF as a stabilizer. The amount of the TBA-DMC catalyst used was an amount such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound 4.

[Example 5]
Polyether compound 5 was produced in the same manner as in Example 1, except that PO(5) was used instead of PO(1).

[Example 6]
Polyether compound 6 was produced in the same manner as in Example 2, except that PO(6) was used instead of PO(2).

[Example 7]
Polyether compound 7 was produced in the same manner as in Example 3, except that PO(7) was used instead of PO(3).

[Example 8]
Polyether compound 8 was produced in the same manner as in Example 4, except that PO(8) was used instead of PO(4).

The content of ultra-high molecular weight components, Mw/Mn, and viscosity of each example of polyether compound are shown in Table 1.

In Example 1, the Mw/Mn and viscosity of the polyether compound are lower than those of Example 5, which has the same initiator and OHV-converted molecular weight.
In Example 2, the Mw/Mn and viscosity of the polyether compound are lower than those of Example 6, which has the same initiator and OHV-converted molecular weight.
In Example 3, the Mw/Mn and viscosity of the polyether compound are lower than those of Example 7, which uses the same initiator and has the same molecular weight calculated as OHV.
In Example 4, the Mw/Mn and viscosity of the polyether compound are lower than those of Example 8, which has the same initiator and OHV-converted molecular weight.
From the above results, it was confirmed that a polyether compound having a narrow molecular weight distribution and low viscosity could be more reliably obtained.

The present invention provides a method for producing polyether compounds that can more reliably produce polyether compounds with narrow molecular weight distribution and low viscosity.

Claims (2)

A method for producing a polyether compound, comprising the steps of:
contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator;
The alkylene oxide-containing feedstock has a methanol content of 0.0001 ppm or more and less than 20 ppm, based on the total mass of the alkylene oxide-containing feedstock. The method according to claim 1, wherein the alkylene oxide content of the alkylene oxide-containing raw material is 99.70% by mass or more.