JPWO2014073580A1 - Method for producing hydroxyl group-containing polyether, method for producing hydrolyzable silyl group-containing polyether, and method for producing urethane prepolymer - Google Patents

Abstract

Provided is a method for producing a hydroxyl group-containing polyether, which can produce a hydroxyl group-containing polyether having a high molecular weight with a smaller molecular weight distribution. In the presence of the double metal cyanide complex catalyst and the polyoxyalkylene compound (Z), a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator having at least one hydroxyl group per molecule, and a weight average molecular weight of 5,000 to A 500,000 hydroxyl-containing polyether is produced. The polyoxyalkylene compound (Z) is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction, and having a weight average molecular weight of the hydroxyl group. It is a polyoxyalkylene compound that is smaller than the containing polyether.

Description

  The present invention relates to a method for producing a hydroxyl group-containing polyether. The present invention also relates to a method for producing a hydrolyzable silyl group-containing polyether and a method for producing a urethane prepolymer using the method for producing a hydroxyl group-containing polyether of the present invention.

  A hydroxyl group-containing polyether obtained by ring-opening addition of a cyclic ether compound to an initiator is used for, for example, a reaction with a polyisocyanate compound to produce a polyurethane such as polyurethane foam or a urethane prepolymer, and a hydrolyzable silyl group. Used for producing hydrolyzable silyl group-containing polyether by reacting the containing compound. Hydroxyl-containing polyethers and derivatives thereof are widely used for other applications such as surfactants and lubricants. Hereinafter, the hydrolyzable silyl group-containing polyether is also referred to as “modified silicone polymer”.

The hydroxyl group-containing polyether is generally produced by a method in which an initiator and a catalyst are charged into a reaction vessel, and a cyclic ether compound is successively supplied thereto to cause a ring-opening addition reaction.
In recent years, in order to improve the physical properties such as strength and elongation of cured products using polymers such as polyurethane and modified silicone polymers, a high molecular weight hydroxyl group-containing polyether, particularly a hydroxyl group-containing polyether having a molecular weight of 15,000 or more is desired. Has been.

Alkali catalysts such as KOH are generally used for the production of a hydroxyl group-containing polyether, but there is a tendency that a certain amount of by-products are generated. When the molecular weight is 10,000 or more, the amount of by-products It is difficult to produce a high molecular weight body. As a method in which a side reaction hardly occurs, a method of producing a high molecular weight hydroxyl group-containing polyether using a double metal cyanide complex catalyst (hereinafter sometimes referred to as “DMC catalyst”) is known.
For example, Patent Document 1 discloses a method of producing a high molecular weight polyol having a low total unsaturation by ring-opening addition reaction of a cyclic ether compound with an initiator in the presence of a glyme-based DMC catalyst in the presence of a solvent. Have been described. However, the molecular weight of the polyols disclosed in the examples is up to 5,000.

As a method for producing a high molecular weight hydroxyl group-containing polyether, a method in which a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator in the presence of an organic solvent has been proposed.
For example, in Patent Document 2, a DMC catalyst is used, and a cyclic ether compound is subjected to ring-opening addition to an initiator in the presence of an organic solvent of 5 parts by weight or less with respect to the obtained hydroxyl group-containing polyether. A method of manufacturing is disclosed. The molecular weight of the hydroxyl group-containing polyether disclosed here is about 10,000, and no example of producing a hydroxyl group-containing polyether of 15,000 or more is described.
Moreover, it does not describe using a polyoxyalkylene compound which does not have a reactive group with respect to the ring-opening addition reaction of a cyclic ether compound instead of an organic solvent.

U.S. Pat. No. 3,829,505 Japanese Patent No. 2946580

In general, in the process of producing a hydroxyl group-containing polyether, when the ring-opening addition reaction of the cyclic ether compound proceeds and the molecular weight of the hydroxyl group-containing polyether increases, the viscosity of the reaction solution increases. When the viscosity of the reaction liquid increases, the cyclic ether compound in the reaction liquid becomes non-uniform and it becomes difficult to obtain uniform reaction, so that the molecular weight distribution tends to be large. Accordingly, only a high molecular weight hydroxyl group-containing polyether having a large molecular weight distribution could be produced. When the molecular weight distribution is large, the physical properties vary greatly, and as a result, the physical properties of the modified silicone polymer and urethane prepolymer obtained by using the hydroxyl group-containing polyether are likely to deteriorate.
The present invention provides a method for producing a hydroxyl group-containing polyether, a method for producing a modified silicone polymer and a method for producing a urethane prepolymer, which can produce a hydroxyl group-containing polyether having a high molecular weight with a smaller molecular weight distribution. provide.

The present invention includes the following [1] to [15].
[1] A cyclic ether compound is subjected to a ring-opening addition reaction with an initiator having at least one hydroxyl group per molecule in the presence of a composite metal cyanide complex catalyst and the following polyoxyalkylene compound (Z), and the weight average molecular weight is A method for producing a 5,000 to 500,000 hydroxyl group-containing polyether,
The polyoxyalkylene compound (Z) is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction, and the weight average molecular weight of which is produced. A method for producing a hydroxyl group-containing polyether, which is a polyoxyalkylene compound smaller than the hydroxyl group-containing polyether.

[2] The hydroxyl group-containing polyether according to [1], wherein 10 to 300 parts by mass of the polyoxyalkylene compound (Z) is present with respect to 100 parts by mass of the hydroxyl group-containing polyether to be produced. Production method.
[3] Production of a hydroxyl group-containing polyether according to [1] or [2], wherein the polyoxyalkylene compound (Z) is a polyoxyalkylene compound having an alkoxy group or an acyloxy group at the end of the polyoxyalkylene chain. Method.
[4] The method for producing a hydroxyl group-containing polyether according to [3], wherein the alkoxy group has 1 to 8 carbon atoms and the acyloxy group has 2 to 8 carbon atoms.
[5] The hydroxyl group-containing polyoxyalkylene compound (z1) in which the polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and has 1 to 3 hydroxyl groups. The method for producing a hydroxyl group-containing polyether according to [3], which is a compound having a molecular weight of 100 to 2000 per terminal group, obtained by converting a hydroxyl group of
[6] The method for producing a hydroxyl group-containing polyether according to any one of [3] to [5], wherein all of the terminal groups are methoxy groups.
[7] The method for producing a hydroxyl group-containing polyether according to any one of [1] to [6], wherein the oxyalkylene group in the polyoxyalkylene compound (Z) is an oxypropylene group.

[8] The weight average molecular weight of the hydroxyl group-containing polyether is 15,000 to 500,000,
The polyoxyalkylene compound (Z) has a hydroxyl group of a hydroxyl group-containing polyoxyalkylene compound (z1) having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups. A polyoxyalkylene compound having a molecular weight of 100 to 1000 per end group, obtained by conversion to an alkoxy group,
The method for producing a hydroxyl group-containing polyether according to [1], wherein 10 to 80 parts by mass of the polyoxyalkylene compound (Z) is present with respect to 100 parts by mass of the hydroxyl group-containing polyether to be produced.
[9] The method for producing a hydroxyl group-containing polyether according to [8], wherein the alkoxy group has 1 to 4 carbon atoms.
[10] The method for producing a hydroxyl group-containing polyether according to [8] or [9], wherein all of the terminal groups are methoxy groups.
[11] The method for producing a hydroxyl group-containing polyether according to any one of [8] to [10], wherein the oxyalkylene group in the polyoxyalkylene compound (Z) is an oxypropylene group.

[12] A step of producing a hydroxyl group-containing polyether by the production method according to any one of [1] to [11],
A method for producing a hydrolyzable silyl group-containing polyether, comprising a step of reacting a hydroxyl group of the obtained hydroxyl group-containing polyether with a hydrolyzable silyl group-containing compound.
[13] The method for producing a hydrolyzable silyl group-containing polyether according to [12], wherein the hydrolyzable silyl group-containing compound is a compound having an isocyanate group and a hydrolyzable silyl group.

[14] A step of producing a hydroxyl group-containing polyether by the production method according to any one of [1] to [11],
The manufacturing method of the urethane prepolymer which has the process of making a polyisocyanate compound react with the obtained hydroxyl-containing polyether.
[15] Hydrolysis characterized in that the urethane prepolymer obtained in [14] and having an isocyanate group is reacted with a compound having an active hydrogen-containing group capable of reacting with an isocyanate group and a hydrolyzable silyl group. For producing a reactive silyl group-containing polyether.

According to the present invention, a hydroxyl group-containing polyether having a high molecular weight and a small molecular weight distribution can be produced.
According to the present invention, a urethane prepolymer or a modified silicone polymer excellent in workability and physical properties can be produced using a hydroxyl group-containing polyether having a high molecular weight and a small molecular weight distribution.

  In the method for producing a hydroxyl group-containing polyether of the present invention, a cyclic ether compound is opened to an initiator having at least one active hydrogen atom per molecule in the presence of a double metal cyanide complex catalyst and a polyoxyalkylene compound (Z). This is a method for producing a hydroxyl group-containing polyether by a cycloaddition reaction.

<Hydroxyl-containing polyether>
The hydroxyl group-containing polyether in the present specification means polyether monool and polyether polyol.
In this specification, the cyclic ether compound is a compound having a heterocycle composed of a carbon atom and one or two oxygen atoms, and the bond between the carbon atom and the oxygen atom is broken to open the ring. And a compound capable of causing a polymerization reaction (that is, a ring-opening addition reaction) by sequentially repeating a reaction of addition to an active hydrogen-containing group such as a hydroxyl group. Hereinafter, the cyclic ether compound is also referred to as a cyclic ether.
Hydroxyl-containing polyether having a polymer chain (polyether chain) composed of a structural unit in which the cyclic ether is opened by a ring-opening addition reaction of the cyclic ether to an initiator having a hydroxyl group, and having a hydroxyl group at the terminal Produces. The polyether monool has one hydroxyl group, and the polyether polyol has two or more hydroxyl groups.
The polyether chain in this specification refers to a structure in which structural units containing an ether bond are linked in a chain.
In this specification, the ring-opening addition reaction may be simply referred to as polymerization. The number of hydroxyl groups of the hydroxyl group-containing polyether obtained by such polymerization is equal to the number of hydroxyl groups of the initiator. When a mixture of two or more initiators having different numbers of hydroxyl groups is used, the average number of hydroxyl groups per molecule of the initiator mixture (sometimes simply referred to as the average number of hydroxyl groups) is one molecule of the resulting hydroxyl group-containing polyether. The average number of hydroxyl groups per unit (sometimes simply referred to as the average number of hydroxyl groups).

In this specification, the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the hydroxyl group-containing polyether are obtained by gel permeation chromatography (GPC) using a polystyrene polymer as a reference. This is the so-called molecular weight in terms of polystyrene.
The hydroxyl value (OHV, unit is mgKOH / g) of the hydroxyl group-containing polyether in the present specification is a value measured according to JIS K1557 (2007 edition).
The average molecular weight in terms of hydroxyl value of the hydroxyl group-containing polyether is a value calculated by using the following formula from the hydroxyl value (OHV) and the average hydroxyl group number f of the initiator used when producing the hydroxyl group-containing polyether. . Hydroxyl value conversion average molecular weight = (56,100 / OHV) × (f)

The weight average molecular weight (Mw) of the hydroxyl group-containing polyether of the present invention is 5,000 to 500,000, preferably 10,000 to 500,000. The higher the molecular weight of the hydroxyl group-containing polyether, the more by-products are more likely to be produced when the hydroxyl group-containing polyether is produced using a double metal cyanide complex catalyst. When the Mw of the hydroxyl group-containing polyether is 5,000 or more, the effect of suppressing the by-product by using the present invention can be sufficiently obtained, and when it is 500,000 or less, the viscosity in use can be kept low. Therefore, it is preferable.
Preferably, the weight average molecular weight (Mw) of the hydroxyl group-containing polyether of the present invention is 15,000 to 500,000, more preferably 20,000 to 300,000, and particularly preferably 25,000 to 100,000. When Mw is 15,000 or more, it is preferable because an effect of improving physical properties such as strength and elongation is obtained, and when it is 500,000 or less, viscosity in use can be suppressed low.
The molecular weight distribution (Mw / Mn) of the hydroxyl group-containing polyether of the present invention is preferably less than 1.20. Since the lower limit of the molecular weight distribution is preferably as small as possible, it becomes difficult to produce. Therefore, in reality, it is more preferably 1.01 or more and less than 1.20, and particularly preferably 1.01 or more and less than 1.15.
The hydroxyl value of the hydroxyl group-containing polyether obtained by the production method of the present invention is preferably 11 mgKOH / g or less, more preferably 6 mgKOH / g or less, and particularly preferably 4 mgKOH / g or less. The lower limit is preferably 0.22 mgKOH / g or more, more preferably 1 mgKOH / g or more, and further preferably 2 mgKOH / g or more in order to keep the viscosity of the hydroxyl group-containing polyether low. The smaller the molecular weight per hydroxyl group, the smaller the molecular weight distribution.

<Double metal cyanide complex catalyst (DMC catalyst)>
A well-known thing can be used for the DMC catalyst in this invention. Typically, it is represented by the following formula (1). M ¹ _a [M ² _b (CN) _c ] _de (M ³ _f X _g ) h (H ₂ O) _i (L) (1) (In formula (1), M ^{1 to} M ³ are Metal, X is a halogen atom, L is an organic ligand, a, b, c, d, e, f, g, h, i are dependent on the valence of the metal, the coordination number of the organic ligand, etc. (The numbers that can change are shown separately.)

In the formula, M ¹ or M ³ represents Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), Selected from the group consisting of V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) And at least one metal atom, preferably Zn (II) or Fe (II). The Roman numeral in parentheses following the atomic symbol of the metal represents the valence, and so on. M ¹ and M ^{3 in} one molecule may be the same as or different from each other. Preferably they are the same as each other.

M ² is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II), V It is at least one metal atom selected from the group consisting of (IV) and V (V), and is preferably Co (III) or Fe (III). X is a halogen atom. L represents an organic ligand.

As the organic ligand, alcohol, ether, ketone, ester, amine, amide and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, One selected from ethylene glycol dimethyl ether (also referred to as glyme), diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane. Or 2 or more types of compounds are mentioned. Dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferred.
Particularly preferred organic ligands are tert-butyl alcohol, tert-pentyl alcohol, ethylene glycol mono-tert-butyl ether, or a combination of tert-butyl alcohol and ethylene glycol mono-tert-butyl ether. When such an organic ligand is used, a particularly high catalytic activity is obtained, which is preferable in terms of narrowing the molecular weight distribution of the hydroxyl group-containing polyether.

Specifically, such a DMC catalyst has the same formula (1) in which M ¹ and M ³ are the same as each other, Zn (II) or Fe (II), and M ² is Co (III) or Fe (III). Wherein X is halogen, L is tert-butyl alcohol or ethylene glycol mono-tert-butyl ether, M ¹ and M ³ are Zn (II), M ² is Co (III), and X is What potassium and L are tert- butyl alcohol is especially preferable at the point which can reduce a by-product.

The manufacturing method of a DMC catalyst is not specifically limited, A well-known method can be used suitably. For example, (i) an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt with a cyanometalate acid and / or an alkali metal cyanometalate in an aqueous solution, and then formed. A method in which a solid component is separated and the separated solid component is further washed with an organic ligand aqueous solution, or (ii) a metal halide salt, a cyanometallate and / or an alkali metal cyanometa in an organic ligand aqueous solution The reaction product (solid component) obtained by reacting with the rate is separated, and the cake (solid component) obtained by the method of washing the separated solid component with an organic ligand aqueous solution is filtered and further separated. The method of making it dry can be mentioned.
The metal constituting the cyano metalate of the alkali metal cyano metalate used in the production of the DMC catalyst corresponds to M ² in the formula (1). As the cyanometalate or alkali metal cyanometalate used as a raw material for producing the DMC catalyst of the present invention, H ₃ [Co (CN) ₆ ], Na ₃ [Co (CN) ₆ ], or K ₃ [Co (CN ₆ ] is preferred, and Na ₃ [Co (CN) ₆ ] or K ₃ [Co (CN) ₆ ] is particularly preferred.

The amount of the DMC catalyst used in the present invention is set to a required amount or more according to the target molecular weight of the hydroxyl group-containing polyether to be produced. On the other hand, it is preferable to use the DMC catalyst as little as possible to reduce the DMC catalyst remaining in the obtained hydroxyl group-containing polyether and the metal compound derived from the DMC catalyst. This can reduce the influence of the residual DMC catalyst on the reaction rate between the hydroxyl group-containing polyether and the polyisocyanate compound and the physical properties of polyurethane products or functional oils produced using the hydroxyl group-containing polyether as a raw material. it can.
Usually, after the cyclic ether is polymerized with the initiator, an operation of removing the DMC catalyst from the obtained hydroxyl group-containing polyether is performed. However, if the amount of DMC catalyst remaining in the hydroxyl group-containing polyether is small and does not adversely affect the subsequent reaction with the polyisocyanate compound and the properties of the final product, the hydroxyl group-containing polyether is used without removing the DMC catalyst. Therefore, the production efficiency of the hydroxyl group-containing polyether can be increased.
Specifically, the total amount of metals (for example, Zn and Co) derived from the DMC catalyst contained in the hydroxyl group-containing polyether at the end of the polymerization reaction is 1 to 30 ppm with respect to 100 parts by mass of the hydroxyl group-containing polyether. It is preferable that the amount is 10 ppm or less, particularly preferably because excellent storage stability can be obtained when a urethane prepolymer or a hydrolyzable silyl group-containing polyether is obtained. When the total amount of metals derived from the DMC catalyst is 30 ppm or less, removal of the remaining catalyst from the obtained hydroxyl group-containing polyether tends to be unnecessary.

<Initiator>
The initiator in the present invention is a compound having at least one hydroxyl group in one molecule. Specifically, a compound having 1 to 12 hydroxyl groups and having a number average molecular weight (Mn) of 18 to 20,000 is preferable. In addition, when it is comprised only from the molecule | numerator of the same molecular weight, such as the low molecular alcohol as an initiator, let the molecular weight calculated | required from chemical formula be a number average molecular weight (Mn).
Specific examples of the initiator include monovalent compounds such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Alcohols; water; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane Dihydric alcohols such as diol and 1,4-cyclohexanediol; glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc. Trihydric or higher polyhydric alcohols; sugars such as glucose, sorbitol, dextrose, fructose, sucrose, methylglucoside, trehalose or derivatives thereof; phenols such as bisphenol A, bisphenol F, bisphenol S, novolac, resole, resorcin, Examples include fatty acid triglycerides having a hydroxyl group such as castor oil and castor oil condensate, and condensates thereof. These compounds can be used alone or in combination of two or more.

Further, a hydroxyl group-containing polyether or polyoxytetramethylene glycol obtained by polymerizing alkylene oxide with these compounds by a known method can also be used as an initiator. These compounds having a polyether chain preferably have a number average molecular weight (Mn) of 300 to 20,000 and a hydroxyl group number of 1 to 12 per molecule.
Further, the hydroxyl value of these compounds is preferably 187 mgKOH / g or less. Furthermore, the compound having a hydroxyl value of 30 mgKOH / g or more higher than the hydroxyl value of the target hydroxyl group-containing polyether is preferable, and a compound having a hydroxyl value of 40 mgKOH / g or more is particularly preferable.

In the present invention, the number average molecular weight (Mn) of the initiator is preferably 300 or more, more preferably 300 to 10,000, more preferably 600 in that the time until the polymerization reaction starts in the presence of a DMC catalyst can be easily shortened. ˜5,000 is particularly preferred.
On the other hand, it is preferable to use an initiator having a number average molecular weight (Mn) of 20,000 or less because the viscosity is not too high when the initiator is charged into the reaction vessel.
The number average molecular weight (Mn) of the initiator is lower than the number average molecular weight (Mn) of the hydroxyl group-containing polyether obtained by using the initiator. The difference between the number average molecular weight of the initiator and the number average molecular weight of the hydroxyl group-containing polyether obtained by using the initiator (that is, the amount of units in which the cyclic ether is opened) is preferably 500 or more, and 1,000 or more. Particularly preferred. When the difference in number average molecular weight is 500 or more, the amount of polymerization in the presence of the DMC catalyst increases, so that it is easy to obtain the merit that the amount of by-products can be reduced by polymerization in the presence of the DMC catalyst.
Generally, the number average molecular weight of the hydroxyl group-containing polyether to be produced is 1.5 times or more and 30 times or less of the number average molecular weight of the initiator used for producing it in relation to the capacity of the stirring tank. Is preferred. However, according to the production method of the present invention, by introducing the polyoxyalkylene compound (Z) together with the initiator before the reaction for producing the hydroxyl group-containing polyether, it is difficult to be limited by the capacity of the stirring tank, and the number of initiators It is easy to produce a hydroxyl group-containing polyether having an average molecular weight of 30 times or more.

  1-12 are preferable, as for the number of hydroxyl groups of an initiator, 1-8 are more preferable, and 1-4 are especially preferable. When an initiator having a hydroxyl number of not more than the upper limit of the above range is used, the molecular weight distribution of the resulting hydroxyl group-containing polyether tends to be narrow. When using 2 or more types of compounds together as an initiator, the average number of hydroxyl groups per molecule is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4. preferable. Further, when the obtained hydroxyl group-containing polyether is used as a raw material for a resin such as polyurethane, the hydroxyl group number of the hydroxyl group-containing polyether is preferably 2 to 8, particularly preferably 2 to 6. Therefore, as an initiator for producing such a hydroxyl group-containing polyether, an initiator having 2 to 8 hydroxyl groups, particularly 2 to 6 hydroxyl groups is preferable. When using 2 or more types of initiator, 1.5-8 are preferable and, as for the average number of hydroxyl groups of an initiator, 1.8-6 are especially preferable.

<Cyclic ether compound>
As the cyclic ether, a compound having an epoxy ring, an oxetane ring or an oxolane ring is preferable. In particular, a compound having one epoxy ring is preferable. As the cyclic ether, alkylene oxide is preferable. Examples of the compound having one epoxy ring other than alkylene oxide include halogen-containing alkylene oxide, cycloalkene oxide such as cyclopentene oxide and cyclohexene oxide, aryl-substituted alkylene oxide such as styrene oxide, glycidyl compound such as glycidyl alkyl ether and glycidyl alkyl ester, Etc. Examples of the compound having an oxetane ring include oxetane, and examples of the compound having an oxolane ring include tetrahydrofuran.

  As the cyclic ether, an alkylene oxide is preferable, and an alkylene oxide having 2 to 20 carbon atoms is particularly preferable. Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and α-olefin oxide having 5 to 20 carbon atoms. One or more selected from the group consisting of these can be used.

Among these alkylene oxides, alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.
The cyclic ether can be determined depending on the target physical properties of the final product using a hydroxyl group-containing polyether as a raw material. However, in the case of using an adhesive, a sealing agent or the like, it is preferable to use only propylene oxide from the viewpoint of water resistance.

In the polymerization step, the cyclic ether may be used alone or in combination of two or more. When two or more kinds of cyclic ethers are subjected to ring-opening addition polymerization to the initiator, a mixture of two or more kinds of cyclic ethers may be subjected to ring-opening addition polymerization to form a random polymer chain, and two or more kinds of cyclic ethers may be separated. May be sequentially subjected to ring-opening addition polymerization to form a block polymer chain. Further, formation of random polymer chains and formation of block polymer chains may be combined.
In the method for producing a hydroxyl group-containing polyether described later, the types of cyclic ethers used in the initial step (a) and the polymerization step (b) may be different. This kind of cyclic ether means not only the kind of cyclic ether but also cyclic ethers having different mixing ratios in the case of a mixture of two or more kinds of cyclic ether compounds.

<Polyoxyalkylene compound (Z)>
The polyoxyalkylene compound (Z) in the present invention is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction with the cyclic ether compound. The polyoxyalkylene compound (Z) converts the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) into an organic group that is inert to the ring-opening addition reaction of the cyclic ether used in the production of the desired hydroxyl group-containing polyether. It is preferable that it is a compound obtained by this. “Converting to an inactive group” means that the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound is converted to a group having no reactive group that the cyclic ether can undergo ring-opening addition.
The weight average molecular weight of the hydroxyl group-containing polyoxyalkylene compound (z1) is smaller than the target hydroxyl group-containing polyether. The difference between the molecular weight of the hydroxyl group-containing polyoxyalkylene compound (z1) and the molecular weight of the target hydroxyl group-containing polyether is preferably 5,000 or more, and more preferably 10,000 or more.
In the present specification, the hydroxyl group-containing polyoxyalkylene compound means a polyoxyalkylene monool or a polyoxyalkylene polyol.
The polyoxyalkylene chain in the hydroxyl group-containing polyoxyalkylene compound (z1) is composed of a chain of oxyalkylene groups formed by a ring-opening addition reaction of alkylene oxide.

The polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms, and the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups. A compound obtained by converting to an organic group inactive to the ring-opening addition reaction of a cyclic ether used for the production of the target hydroxyl group-containing polyether is preferable.
Such inactive organic group conversion methods include conversion to an alkoxy group with an alkyl halide (alkoxylation), monocarboxylic acid (such as acetic acid), monocarboxylic acid anhydride (such as acetic anhydride), acyl halide (salt chloride) Examples include, but are not limited to, conversion to an acyloxy group (esterification) with a monocarboxylic acid such as acetyl) or a reactive derivative thereof (esterification), urethanization with a monoisocyanate compound, halogenation with phosphorus trichloride, and the like. These methods may use two or more conversion methods in combination. Considering the influence during the production of the hydroxyl group-containing polyether, the number of carbon atoms of the alkyl halide, monocarboxylic acid, or monoisocyanate compound used for the conversion is preferably 8 or less.
A method of converting a hydroxyl group to an alkoxy group by alkoxylation, or converting a hydroxyl group to an acyloxy group (—O—C (O) —R ′; R ′ is an alkyl group, etc.) by esterification with a monocarboxylic acid or a reactive derivative thereof. Is preferred.

The conversion method is preferably at least one selected from the group consisting of alkoxylation and esterification in view of the influence during production of the hydroxyl group-containing polyether and production efficiency.
When the hydroxyl group-containing polyoxyalkylene compound (z1) has two or more hydroxyl groups, each hydroxyl group may be converted into a different inert organic group. In this case, it is preferable that a part of the hydroxyl group is converted into an alkoxy group and the other hydroxyl group is converted into an acyl group and / or an acyloxy group. When using alkoxylation and esterification together, it is preferable that the total number of moles of esterified terminal hydroxyl groups is 50 mol% or less with respect to the number of moles of alkoxylated terminal hydroxyl groups.
From the viewpoint of hydrolysis resistance, it is most preferable to convert all hydroxyl groups of the hydroxyl group-containing polyoxyalkylene compound (z1) into alkoxy groups.

When the terminal group of the polyoxyalkylene compound (Z) is an alkoxy group (—OR ¹⁰ , R ¹⁰ is an alkyl group), the alkoxy group preferably has 1 to 8 carbon atoms (the carbon number of R ¹⁰ ). 4 is more preferable, and 1-2 is more preferable.
When the terminal group of the polyoxyalkylene compound (Z) is an acyloxy group, the acyloxy group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2.
It is preferable that the alkoxy group has 8 or less carbon atoms in that the effect of narrowing the molecular weight by producing the hydroxyl group-containing polyether in the presence of the polyoxyalkylene compound (Z) can be sufficiently obtained. In particular, the number of carbon atoms of 4 or less is preferable because the oxyalkylene group content in the polyoxyalkylene compound (Z) is high. In particular, it is preferable that all of the alkoxy groups present at the terminals of the polyoxyalkylene compound (Z) are methoxy groups because the oxyalkylene group content in the polyoxyalkylene compound is high. The higher the oxyalkylene group content, the better the compatibility with the hydroxyl group-containing polyether.
On the other hand, aromatic, alicyclic or aliphatic dicarboxylic acids represented by dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, dioctyl adipate, dioctyl hexahydrophthalate and the like, which are known as plasticizers for general resins, An ester compound of an alcohol (an ester compound having no polyoxyalkylene chain) is not preferred because it may be different from the polyoxyalkylene compound in the possibility of side reactions during production and in polarity with a hydroxyl group-containing polyether. .

[Conversion rate of terminal group]
The conversion rate when converting the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) to the inactive organic group is not necessarily 100%. Specifically, it is preferable to convert 50 mol% or more of the hydroxyl group into an active organic group, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The higher conversion rate is preferable in that alkylene oxide addition to the unconverted hydroxyl group of the polyoxyalkylene compound (Z) is less likely to occur during the production of the hydroxyl group-containing polyether. When ring-opening addition of an alkylene oxide cyclic ether to such an unconverted hydroxyl group occurs, a hydroxyl group-containing polyether having a target molecular weight cannot be obtained, and a dilution effect by the polyoxyalkylene compound (Z) cannot be obtained. May occur.

In the present invention, the presence of the polyoxyalkylene compound (Z) in the reaction solution for producing a high molecular weight hydroxyl group-containing polyether using a DMC catalyst makes the molecular weight distribution narrower even if the molecular weight is the same. A hydroxyl group-containing polyether is obtained. In the method for producing a hydroxyl group-containing polyether of the present invention, both the hydroxyl group-containing polyether as a reaction product and the polyoxyalkylene compound (Z) have a polyether chain, thereby improving the compatibility of both in the reaction solution. As a result, it is considered that the uniformity of the reaction is good and the molecular weight distribution becomes smaller.
In the production of the hydroxyl group-containing polyether, the polyether chain contained in the hydroxyl group-containing polyether and the polyoxyalkylene chain contained in the polyoxyalkylene compound (Z) are preferably polyether chains derived from the same alkylene oxide. .

When the hydroxyl group-containing polyoxyalkylene compound (z1) has one hydroxyl group, the terminal having no hydroxyl group in the polyoxyalkylene chain may be an inert organic group such as an alkoxy group or an alkoxycarbonyl group. For example, a polyoxyalkylene monool obtained by polymerizing a cyclic ether with an alkane monool using an alkane monool as an initiator has an alkoxy group, and is similarly obtained by polymerizing a cyclic ether with a monocarboxylic acid. The polyoxyalkylene monool has an acyloxy group. The inactive terminal group of the polyoxyalkylene compound (Z) is a hydroxyl group-containing polyoxyalkylene compound (z1) other than the inactive organic group generated by inactivating the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1). It shall contain the inert organic groups it had. Therefore, the terminal group of the polyoxyalkylene compound (Z) refers to both the inactive organic group possessed by the hydroxyl group-containing polyoxyalkylene compound (z1) and the inert organic group obtained by converting the hydroxyl group. means. Therefore, the number of end groups of the polyoxyalkylene compound (Z) is 2 or more.
The hydroxyl group-containing polyoxyalkylene compound (z1) obtained by using a hydroxyl group-containing compound having one or two hydroxyl groups as an initiator is a linear structure compound having one or two hydroxyl groups. The polyoxyalkylene compound (Z) obtained from the hydroxyl group-containing polyoxyalkylene compound (z1) is similarly a compound having a structure. Regardless of the difference in the number of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene compound (z1), the number of terminal groups of these compounds having a linear structure is 2 in the present invention. When the number of hydroxyl groups in the initiator is 3 or more, the resulting hydroxyl group-containing polyoxyalkylene compound (z1) has the same number of end groups as the number of hydroxyl groups in the initiator.

  The molecular weight per terminal group of the polyoxyalkylene compound (Z) is preferably from 100 to 2,000, more preferably from 100 to 1,000, and even more preferably from 150 to 800. When the molecular weight is 100 or more, the volatility of the polyoxyalkylene compound (Z) tends to be sufficiently low. If it is 2,000 or less, the dilution effect is increased. Particularly when the viscosity is 1,000 or less, the viscosity of the reaction solution tends to be sufficiently low.

The hydroxyl group-containing polyoxyalkylene compound (z1) used for the synthesis of the polyoxyalkylene compound (Z) is obtained by ring-opening addition of an alkylene oxide having 2 to 4 carbon atoms to an initiator having 1 to 3 hydroxyl groups. The resulting hydroxyl group-containing polyoxyalkylene compound is preferred.
Among the compounds that can be used as the initiator of the above-mentioned hydroxyl group-containing polyether, those having no polyoxyalkylene chain and having 1 to 3 hydroxyl groups can be used as the initiator.
Of the compounds that can be used as the initiator of the hydroxyl group-containing polyether described above, the polyoxyalkylene chain has a polyoxyalkylene chain, and the polyoxyalkylene chain is derived from an alkylene oxide having 2 to 4 carbon atoms, and The initiator having 1 to 3 hydroxyl groups can be used as an initiator for synthesizing the hydroxyl group-containing compound (z1), the hydroxyl group-containing polyoxyalkylene compound (z1), or the hydroxyl group-containing polyoxyalkylene compound (z1) itself.
The molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is 18 or more, preferably 32 or more. The upper limit of the molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably 1,000 or less and more preferably 300 or less because the oxyalkylene group content in the hydroxyl group-containing polyoxyalkylene compound (z1) is high. preferable.

Examples of the initiator having 1 hydroxyl group include methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Monohydric alcohols are preferred. When a monohydric alcohol (R ¹¹ —OH) is used as an initiator, an alkoxy group (R ¹¹ O—) derived from the monohydric alcohol is present at the end group of the resulting polyoxyalkylene compound (Z). Exists. Therefore, the number of carbon atoms of the monohydric alcohol (R ¹¹ —OH) as the initiator is preferably 1 to 4, and more preferably 1.
As described above, a compound obtained by alkoxylating a terminal hydroxyl group of polyoxyalkylene monool obtained by ring-opening addition of alkylene oxide to an initiator having one hydroxyl group is a compound having alkoxy groups at both ends of one molecule. It becomes.

Examples of the initiator having 2 hydroxyl groups include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4- Dihydric alcohols such as butanediol, 1,6-hexanediol and 1,4-cyclohexanediol are preferred. Of these, water, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol having a relatively low molecular weight of the initiator are more preferable, and propylene glycol and dipropylene glycol are particularly preferable in that the ether group content can be increased.
As the initiator having 3 hydroxyl groups, trihydric alcohols such as glycerin and trimethylolpropane are preferable. Of these, glycerin having a relatively low molecular weight of the initiator is particularly preferred in that the ether group content can be increased.
Examples of the initiator having 4 or more hydroxyl groups include tetrahydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, polyglycerin; glucose, sorbitol, dextrose, fructose, sucrose, methyl Saccharides such as glucoside and trehalose or derivatives thereof are preferred.

The alkylene oxide used for the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably an alkylene oxide having 2 to 4 carbon atoms.
The alkylene oxide used in the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is more preferably the same alkylene oxide as the cyclic ether used in the production of the hydroxyl group-containing polyether, specifically, ethylene oxide, propylene oxide, One or more selected from the group consisting of 1,2-butylene oxide and 2,3-butylene oxide are used. Among these, it is preferable to use ethylene oxide and / or propylene oxide in that the oxyalkylene group content can be increased. Particularly, when the obtained hydroxyl group-containing polyether is used as an adhesive or a sealing agent, the hydroxyl group-containing group is contained. In view of the fact that only propylene oxide is often used in the production of the polyether, it is preferable to use only propylene oxide as the alkylene oxide.
The step of obtaining the hydroxyl group-containing polyoxyalkylene compound (z1) by ring-opening addition of alkylene oxide to the initiator can be carried out by a known method. Usually, a catalyst is used. A catalyst is not specifically limited, A well-known catalyst can be used suitably. An alkali catalyst such as KOH or the above-mentioned DMC catalyst may be used.

The step of alkoxylating the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) can be carried out by a known method. For example, the hydroxyl group (—OH) of the hydroxyl group-containing polyoxyalkylene compound (z1) is alcoholated by a known method to form —OM (M is an alkali metal), and then an alkyl halide (R ¹⁰ —X: X is a halogen atom) ) Can be substituted with an alkoxy group (—OR ¹⁰ ). The halogen atom (X) of the alkyl halide is preferably a chlorine atom (Cl) from the viewpoint of reaction efficiency in the process.
Further, when the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) is esterified, it can be similarly carried out by a known method.

In the method for producing a hydroxyl group-containing polyether of the present invention, the polyoxyalkylene compound (Z) is preferably used in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyether to be produced. The amount of hydroxyl group-containing polyether produced corresponds to the total amount of initiator and reacted cyclic ether.
When the amount of the polyoxyalkylene compound (Z) used is less than 10 parts by mass, the effect of reducing the viscosity of the reaction solution due to the presence of the polyoxyalkylene compound (Z) and the effect of narrowing the molecular weight distribution of the resulting hydroxyl group-containing polyether are obtained. When the amount exceeds 300 parts by mass, the ratio of the polyoxyalkylene compound (Z) is too large, and it is difficult to obtain the desired physical properties of the modified silicone polymer or urethane prepolymer produced using the hydroxyl group-containing polyether. Preferably it is 5-100 mass parts, 10-80 mass parts is more preferable, 15-40 mass parts is further more preferable.

  In the method for producing a hydroxyl group-containing polyether of the present invention, the polyoxyalkylene compound (Z) is added to the reaction system at a time until the polymerization step of the hydroxyl group-containing polyether is completed, Although it can be added in batches, it is preferable to add the whole amount together with the initiator and the DMC catalyst before starting the reaction.

The polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and alkoxylates the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups. The compound is preferably a
In particular, the molecular weight per terminal group of the polyoxyalkylene compound (Z) is preferably 100 to 1,000, and more preferably 150 to 800.
In particular, the amount of the polyoxyalkylene compound (Z) used is preferably 10 to 80 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 15 to 40 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyether produced. preferable.

<Method for producing hydroxyl group-containing polyether>
A preferred method for producing the hydroxyl group-containing polyether of the present invention is a part of a cyclic ether that causes the initiator to undergo a ring-opening addition reaction to a reaction solution containing an initiator and a DMC catalyst (hereinafter sometimes referred to as a cyclic ether for an initial step). .) In an amount of 5 to 20 parts by mass with respect to 100 parts by mass of the initiator contained in the reaction solution, and after the initial step (a), a cyclic ether And a polymerization step (b) in which a polymerization reaction is carried out by additionally supplying.
This method is preferably carried out batchwise, but may be a continuous method. Specifically, it can be carried out as follows.

The mixing means in the initial step (a) of the production method of the present invention is not particularly limited as long as it is a means capable of sufficiently mixing the DMC catalyst and the initiator (including other components used as necessary). Usually, a stirring means is used as the mixing means.
Specific examples of the stirring means in the initial step (a) include stirring blades, bubbling with an inert gas such as nitrogen gas, stirring by electromagnetic waves, ultrasonic waves, and the like, but stirring by stirring blades is preferable.
The shape and material of the pressure-resistant reaction vessel used in the initial step (a) are not particularly limited, but the material is preferably a heat-resistant glass or metal vessel.

First, an initiator, a DMC catalyst, and preferably a polyoxyalkylene compound (Z) are supplied into a pressure-resistant reaction vessel, and before supplying the cyclic ether for the initial step, the gas phase in the pressure-resistant reaction vessel is nitrogen or polymerized. Substitution with a cyclic ether is preferred. Thereby, oxygen in the reaction solution is removed.
Next, the reaction liquid is heated while being stirred, and then heated, and then the initial stage cyclic ether is supplied and reacted in a state where the temperature of the reaction liquid is at a predetermined initial temperature. The initial temperature in this specification refers to the temperature of the reaction liquid at the start of the supply of the cyclic ether for the initial step. The initial temperature of the reaction solution is 120 to 165 ° C, preferably 125 to 150 ° C, particularly preferably 130 to 140 ° C. When the initial temperature is not less than the lower limit of the above range, the catalytic activity is remarkably improved, and when it is not more than the upper limit of the above range, there is no fear that the components contained in the reaction solution are thermally decomposed.
Specifically, it is preferable that the temperature of the reaction liquid is increased to the initial temperature while stirring, and the supply of the cyclic ether is started in a state where the temperature of the reaction liquid is maintained. For example, when the reaction liquid reaches a predetermined initial temperature, the heating is stopped, and the supply of cyclic ether is started before the temperature of the reaction liquid starts to drop.

  The cyclic ether for the initial step is a cyclic ether that is polymerized to an initiator in the production of a hydroxyl group-containing polyether. If the supply amount of the cyclic ether for the initial step is too small, the activation of the DMC catalyst becomes insufficient, and if it is too large, a runaway reaction occurs. Therefore, it is 5-20 mass parts with respect to 100 mass parts of the initiator contained in a reaction liquid. 8-15 mass parts is preferable and 10-12 mass parts is especially preferable.

  The cyclic ether for the initial process is supplied in a state where the pressure-resistant reaction vessel is sealed. When the cyclic ether is supplied to the reaction solution, immediately after that, the internal pressure of the pressure-resistant reaction vessel rises as the unreacted cyclic ether is vaporized. Next, when the DMC catalyst is initially activated, a reaction between the cyclic ether and the initiator occurs, and the internal pressure of the pressure-resistant reaction vessel begins to decrease, and at the same time, the temperature of the reaction solution rises due to reaction heat. When the total amount of the supplied cyclic ether has been reacted, the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the supply, and the temperature of the reaction liquid is not increased by the reaction heat. Depending on the amount of the organic solvent, there is almost no increase in the temperature of the reaction solution due to the heat of reaction, and an increase in internal pressure may be observed. The initial step (a) in the present specification refers to a step from the start of the supply of the cyclic ether for the initial step to the end of the reaction of the cyclic ether. Completion of the reaction of the cyclic ether for the initial step can be confirmed by a decrease in the internal pressure of the pressure resistant reaction vessel. That is, the end of the initial step (a) refers to the time when the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the cyclic ether supply.

Polymerization step (b)
After completion of the initial step, the cyclic ether is newly supplied to the reaction system, the temperature of the reaction solution is adjusted to a predetermined polymerization temperature, and the polymerization reaction is carried out with stirring to obtain the target hydroxyl group-containing polyether.
As the heat-resistant reaction vessel used in the polymerization step (b), a pressure-resistant autoclave vessel is preferably used. The material is not particularly limited. As the reaction vessel, the vessel used in the initial step (a) can be used as it is.

  In the polymerization step (b) of the production method of the present invention, in the presence of a DMC catalyst, when the product of the initial step (a) (a compound obtained by reacting a cyclic ether with an initiator) and the cyclic ether are reacted, As in (a), it is preferable to stir the reaction solution. Propeller blades, paddle blades, Max Blend (registered trademark) blades (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), full zone (registered trademark) blades (manufactured by Shinko Environmental Solution Co., Ltd.), disk turbines, and reaction vessels In order to uniformly mix the inside, a large blade such as a Max Blend blade or a full zone blade is preferable. In addition, dispersers, homomixers, colloid mills, nauter mixers, and the like used for emulsification and dispersion can also be used. Moreover, you may use the mixing by an ultrasonic wave without using a stirring blade. These stirring methods may be used in combination. When using a general stirring method using a stirring blade, increase the rotation speed of the stirring blade as much as possible so long as the gas in the gas phase of the reaction vessel is not taken into the reaction liquid and the stirring efficiency does not decrease. It is preferable to do.

  The polymerization method in the polymerization step (b) is preferably a batch method, but the addition of a mixture containing the cyclic ether and the product of the initial step (a) and the DMC catalyst and the hydroxyl group which is the product of the polymerization step (b) It can also be carried out by a continuous process in which the contained polyether is extracted simultaneously. In particular, the use of the polyoxyalkylene compound (Z) can reduce the viscosity of the entire system, and therefore, when the average molecular weight of the initiator is 300 or less, the continuous method is preferable because of high productivity.

  125-180 degreeC is preferable and, as for the temperature (polymerization temperature) of the reaction liquid at the time of making cyclic ether react in a superposition | polymerization process (b), 125-160 degreeC is especially preferable. When the polymerization temperature is not less than the lower limit of the above range, an appropriate reaction rate can be obtained, and the remaining amount of unreacted product in the final product can be lowered. Moreover, the high activity of a DMC catalyst is appropriately maintained as it is below the upper limit of the said range, and molecular weight distribution can be made small. After the reaction of the cyclic ether in the polymerization step (b) is completed, it is preferable to cool the reaction solution and purify the reaction product.

  The feed rate of the cyclic ether in the polymerization step (b) is preferably as slow as possible because the molecular weight distribution of the resulting polymer can be narrowed. However, since production efficiency is lowered, it is preferable to compare them. As a specific supply rate, 1 to 200% by mass / hour is preferable with respect to the total mass of the hydroxyl group-containing polyether planned as the final product. The supply rate during the polymerization reaction may be changed gradually.

  In addition, you may perform the removal process of a DMC catalyst, and the deactivation process of a DMC catalyst as needed from the reaction liquid obtained after finishing a polymerization process (b). As the method, for example, an adsorption method using an adsorbent selected from synthetic silicate (magnesium silicate, aluminum silicate, etc.), ion exchange resin, activated clay, amine, alkali metal hydroxide, phosphoric acid, A neutralization method using an organic acid such as lactic acid, succinic acid, adipic acid, or acetic acid or a salt thereof, or an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid, or a method that uses a neutralization method and an adsorption method together can be used. When primary hydroxylation using the alkali metal catalyst is performed, the alkali metal catalyst can be similarly deactivated and removed.

According to the method for producing a hydroxyl group-containing polyether of the present invention, a composition containing the target hydroxyl group-containing polyether and a polyoxyalkylene compound (Z) is obtained. When the composition contains a polyoxyalkylene compound (Z), the viscosity is lowered, and therefore, it is preferable in terms of easy handling when used as a raw material for a urethane prepolymer or a modified silicone polymer.
Further, a stabilizer may be added to the composition as necessary in order to prevent deterioration during long-term storage. Examples of the stabilizer include hindered phenol antioxidants such as BHT (dibutylhydroxyl toluene) and octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

According to the production method of the present invention, the polyoxyalkylene compound (Z) is contained in the reaction solution when producing a high molecular weight hydroxyl group-containing polyether using a DMC catalyst, as shown in the Examples below. Thus, a hydroxyl group-containing polyether having a narrower molecular weight distribution can be obtained even if the molecular weight is the same.
In addition, as shown in the comparative examples described later, the use of the polyoxyalkylene compound (Z) has a greater effect of reducing the molecular weight distribution than when an organic solvent is used instead of the polyoxyalkylene compound (Z). When an ester compound having an aromatic ring is used instead of the polyoxyalkylene compound (Z), the effect of reducing the molecular weight distribution cannot be obtained.
Therefore, in the production method of the present invention, the polyoxyalkylene compound (Z) is used in addition to the polyoxyalkylene compound (Z) in addition to the effect of reducing the molecular weight distribution due to the reduced viscosity of the reaction solution. It is thought that having a chain contributes to the reduction of the molecular weight distribution. For example, the hydroxyl group-containing polyether as a reaction product and the polyoxyalkylene compound (Z) both have a polyether chain (polyoxyalkylene chain), thereby improving the compatibility of the two in the reaction solution. As a result, it is considered that the uniformity of the reaction becomes good and the molecular weight distribution becomes smaller.
Moreover, since the polyoxyalkylene compound (Z) of the present invention does not have a hydroxyl group, the reaction is not affected when a hydroxyl group-containing polyether is used as a raw material for a urethane prepolymer or a modified silicone polymer.

<Application>
The hydroxyl group-containing polyether obtained by the production method of the present invention can be made into various polyurethane products by reacting with a polyisocyanate compound and optionally a chain extender. The number of hydroxyl groups of the hydroxyl group-containing polyether used for the polyurethane raw material is preferably 2-8.
The hydroxyl group-containing polyether obtained by the production method of the present invention can be used as a polyol for flexible polyurethane foam. In the production of flexible polyurethane foams, particularly when the hydroxyl group-containing polyether has a high molecular weight and a small molecular weight distribution, good foam appearance, physical properties and vibration characteristics are easily obtained.

  The hydroxyl group-containing polyether obtained by the production method of the present invention is a functional oil agent such as grease base oil, compressor oil, rolling oil, gear oil, metalworking oil, traction drive oil, engine oil, and drilling oil; Alternatively, it can be used as a surfactant or the like, or as a raw material thereof. In these applications, particularly when the hydroxyl group-containing polyether has a high molecular weight and a small molecular weight distribution, improvement in lubricity, detergency and life can be expected.

  The hydroxyl group-containing polyether obtained by the production method of the present invention can also be used as a raw material for the modified silicone polymer. Moreover, it can be made to react with polyisocyanate to make a urethane prepolymer. The modified silicone polymer and urethane prepolymer can be produced by the method described below. The modified silicone polymer and the urethane prepolymer can be suitably used as a curing component of the curable composition for a sealing material. In the curable composition for sealing materials, when the modified silicone polymer and urethane prepolymer constituting the curing component have a high molecular weight and a small molecular weight distribution, the curability is improved particularly including the inside of the sealing material, and the viscosity Therefore, workability is improved. Furthermore, since the molecular weight is uniform, the mechanical properties and durability after curing are excellent.

<Hydrolysable silyl group-containing polyether>
The hydrolyzable silyl group-containing polyether in the present invention has a structure in which a hydrolyzable silyl group represented by the following formula (1) is introduced to the end of the hydroxyl group-containing polyether via a linking group. is there. As described above, the modified silicone polymer refers to this hydrolyzable silyl group-containing polyether.
-SiX _a R ¹ _3-a (1)
In formula (1), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3. However, when a plurality of R ¹ are present, they may be the same or different, and when a plurality of X are present, they may be the same or different.

Examples of the hydrolyzable group as X in the formula (1) include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, and a hydride group.
Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. X is preferably a lower alkoxy group having 4 or less carbon atoms, particularly preferably a methoxy group, an ethoxy group, a propoxy group or a propenyloxy group.

R ¹ in formula (1) is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

<Method for producing hydrolyzable silyl group-containing polyether>
The hydrolyzable silyl group-containing polyether in the present invention has a step of producing a hydroxyl group-containing polyether by the production method of the present invention and a step of introducing a hydrolyzable silyl group into the molecular terminal of the hydroxyl group-containing polyether. It can be manufactured by the method.
As a method for introducing a hydrolyzable silyl group into the molecular terminal of the hydroxyl group-containing polyether, a known method can be used. For example, the following methods (i) to (iv) can be used.

[Method (i)]
In the polymerization step (b), a hydrolyzable silyl group can be introduced by producing a hydroxyl group-containing polyether, introducing an olefin group at the end thereof, and then reacting the hydrosilyl compound represented by the following formula (2).
HSiX _a R ¹ _3-a (2)
In formula (2), R ¹ , X and a are the same as above.
As a method for introducing an olefin group into a hydroxyl group-containing polyether, for example, a method of reacting a compound having a functional group that reacts with a hydroxyl group and an olefin group with the hydroxyl group of the hydroxyl group-containing polyether can be used. In particular, a method in which a hydroxyl group is converted to an alkenyloxy group by alcoholating the hydroxyl group and reacting it with a halogenated alkene (for example, allyl chloride) is preferable.

[Method (ii)]
In the polymerization step (b), when the cyclic ether compound is subjected to ring-opening addition to the initiator, an olefin group-containing epoxy compound such as allyl glycidyl ether is polymerized in combination with another cyclic ether such as alkylene oxide as the cyclic ether compound. Thus, an allyl group-modified hydroxyl group-containing polyether in which an olefin group (for example, an allyl group) is introduced into the hydroxyl group-containing polyether is produced, and this is reacted with the hydrosilyl compound represented by the above formula (2). Degradable silyl groups can be introduced.

[Method (iii)]
In the polymerization step (b), a hydroxyl group-containing polyether is produced, and this is reacted with a polyisocyanate group and a compound having a hydrolyzable silyl group represented by the above formula (1). Can be introduced.

[Method (iv)]
By the method of (i) or (ii) above, a hydroxyl group-containing polyether having an olefin group introduced at the terminal is obtained, and the olefin group and a mercapto group (—SH) of a silicon compound represented by the following formula (3) Can be reacted to introduce a hydrolyzable silyl group.
R ¹ _3-a -SiX _a -R ² SH (3)
In formula (3), R ¹ , X and a are the same as described above, and R ² is a divalent organic group.

[Method (v)]
In the polymerization step (b), a hydroxyl group-containing polyether is produced and reacted with a polyisocyanate group to obtain an isocyanate-terminated urethane prepolymer, and then an active hydrogen-containing group capable of reacting with an isocyanate group such as an amino group. A hydrolyzable silyl group can be introduced by reacting with a compound having a hydrolyzable silyl group represented by the formula (1).
For example, a hydrolyzable silyl group can be introduced by reacting a W group of a silicon compound represented by the following formula (4) with an isocyanate group of a urethane prepolymer having an isocyanate group at a terminal described later.
R ¹ _3-a- SiX _a -R ² W (4)
In formula (4), R ¹ , X and a are the same as above, R ² is a divalent organic group, W is an active hydrogen selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary). It is a containing group.

<Method for producing urethane prepolymer and method for producing hydrolyzable silyl group-containing polyether using the same>
The method for producing a urethane prepolymer of the present invention includes a step of producing a hydroxyl group-containing polyether by the production method of the present invention, and a urethane having an isocyanate group or a hydroxyl group at the terminal by reacting the hydroxyl group-containing polyether with a polyisocyanate compound. A step of obtaining a prepolymer.
By reacting the hydroxyl group-containing polyether with the polyisocyanate compound in an excess ratio of the isocyanate group, a urethane prepolymer having an isocyanate group at the terminal is obtained, and by reacting the hydroxyl group in an excess ratio of the hydroxyl group, the terminal has a hydroxyl group. A urethane prepolymer is obtained. This step can be performed using a known method.
Hydrolyzable silyl group-containing polyether from the urethane prepolymer by a method comprising a step of producing a urethane prepolymer by the production method of the present invention and a step of introducing a hydrolyzable silyl group into the molecular terminal of the urethane prepolymer. Can also be manufactured.

  Examples of the polyisocyanate compound include aromatic poly (polynaphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate). Isocyanates; Aralkyl polyisocyanates such as xylylene diisocyanate and tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate An alicyclic polyisocyanate such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate); Urethane modified product obtained from isocyanate compounds, biuret modified compounds, allophanate modified body, carbodiimide modified body, and isocyanurate-modified products thereof.

Of these, those having two isocyanate groups are preferred, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4′-diphenylmethane diisocyanate are preferred.
The obtained urethane prepolymer can be used as a raw material for urethane-based sealing materials and as a raw material for cast urethane.

Since the hydroxyl group-containing polyether produced by the method for producing a hydroxyl group-containing polyether of the present invention has a high molecular weight, the molecular weight distribution is smaller than the conventional one and the variation in physical properties is small. Can produce a urethane prepolymer or a modified silicone polymer with excellent properties.
In addition, since the hydroxyl group-containing polyether produced by the method for producing a hydroxyl group-containing polyether of the present invention is reduced in viscosity by the polyoxyalkylene compound (Z), a modified silicone polymer or urethane prepolymer is produced using this. By doing so, it is possible to obtain a modified silicone polymer or urethane prepolymer having a high molecular weight but a lower viscosity than the conventional one.
Therefore, it is possible to obtain a high molecular weight modified silicone polymer or urethane prepolymer having a viscosity suitable for use, which has not been suitable for use because of its high viscosity.
When the modified silicone polymer is lowered in viscosity, the coating property is improved. Further, when the molecular weight of the modified silicone polymer is high, the cured product has excellent mechanical properties such as strength and elongation. Such a modified silicone polymer is particularly suitable for a sealing material.
The urethane prepolymer can be used as an adhesive or a sealing agent without being a modified silicone polymer.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
<Measurement method>
[Hydroxyl value]
Hydroxyl groups of polyols were esterified with a pyridine solution of phthalic anhydride and measured by a titration method using a sodium hydroxide (NaOH) solution (based on JIS K1557 (2007 edition)).

[Number average molecular weight (Mn) and weight average molecular weight (Mw)]
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of a polyether such as a hydroxyl group-containing polyether are as follows using a calibration curve prepared using a standard polystyrene sample with a known molecular weight: It is a polystyrene conversion molecular weight obtained by measuring by gel permeation chromatography (GPC) under the conditions of
[GPC measurement conditions]
Model used: HLC-8220GPC (manufactured by Tosoh Corporation)
Data processing device: SC-8020 (manufactured by Tosoh Corporation)
Column used: TSG gel G2500H (manufactured by Tosoh Corporation)
Column temperature: 40 ° C., detector: RI, solvent: tetrohydrofuran, flow rate 0.6 ml / min, sample concentration: 0.5% by mass, injection amount: 10 μl
Standard sample for preparing calibration curve: Polystyrene ([Easical] PS-2 [Polystyrene Standards], manufactured by Polymer Laboratories)
[viscosity]
In accordance with JIS K1557, an E-type viscometer VISCONIC EHD type (manufactured by Tokimec) was used. Measurement was performed using one rotor. The measurement temperature was measured at 25 ° C. unless otherwise specified.

<Production of DMC catalyst>
[Reference Example 1: Production of DMC catalyst slurry]
The polyol X used in this example was produced by subjecting propylene oxide to ring-opening addition reaction to propylene glycol using a potassium hydroxide (KOH) catalyst, and further purifying by a known method. Polyoxypropylene diol having an average molecular weight (Mn) of 1,000 and a hydroxyl value of 112 mgKOH / g.

First, an aqueous zinc chloride solution consisting of 10.2 g of zinc chloride and 10 g of ion-exchanged water was prepared in a 500 mL flask and stirred at 300 rpm while keeping the temperature at 40 ° C. To this, an aqueous solution composed of 4.2 g of potassium hexacyanocobaltate [K ₃ Co (CN) ₆ ] and 75 g of ion-exchanged water was dropped over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then a mixture composed of 80 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of ion-exchanged water, and 0.6 g of polyol X was added, and the mixture was stirred at 40 ° C. for 30 minutes. The mixture was further stirred at 60 ° C. for 60 minutes. The obtained mixture was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC), and the composite metal cyanide complex was obtained in 50 minutes. A solid (cake) containing was obtained.

  Next, the obtained cake was transferred to a flask, a mixed solution consisting of 36 g of TBA and 84 g of ion-exchanged water was added and stirred for 30 minutes, and then pressure filtration was performed for 15 minutes under the same conditions as above, and the cake was again obtained. Got. The cake was transferred to a flask, and a mixed solution composed of 108 g of TBA and 12 g of ion-exchanged water was added and stirred for 30 minutes to obtain a slurry containing a double metal cyanide complex.

To this slurry, 100 g of polyol X was added and dried under reduced pressure at 80 ° C. for 3 hours and further at 115 ° C. for 4 hours, and a slurry of a composite metal cyanide complex catalyst having TBA as an organic ligand (slurry catalyst (s) ) The concentration of the double metal cyanide complex catalyst in the slurry catalyst (s) was 4.1% by mass. In the formula (1), M ¹ and M ³ are Zn, M ² is Co, and L is TBA.

<Production of polyoxyalkylene compound (Z)>
[Production Example 1: Production of polyoxyalkylene compound (Z-1)]
A pressure resistant reaction vessel (capacity 5 L) made of stainless steel (JIS-SUS-316) equipped with a stirrer and capable of controlling the temperature of the reaction solution was used. Specifically, the pressure-resistant reaction vessel includes a stirrer to which one set of anchor blades and two sets of 45 ° inclined two-blade paddle blades are attached, and a heating tank through which a heat medium flows is provided around the vessel. A cooling pipe through which cooling water flows is provided inside the container. The temperature of the reaction solution was measured by a method of measuring the solution temperature with a thermometer installed at the lower part inside the pressure resistant reaction vessel.

First, 670 g of dipropylene glycol and 11 g of solid potassium hydroxide as a propylene oxide addition catalyst were charged into a pressure resistant reactor. Next, after replacing the inside of the pressure resistant reactor with nitrogen, the reaction solution was heated with stirring. When the temperature reached 105 ° C., the heating was stopped, the liquid temperature was maintained at 105 ° C., and while continuing stirring, 2880 g of propylene oxide was fed over 6 hours to react to produce polyoxypropylene diol.
After the supply of propylene oxide was completed, after confirming that the pressure in the pressure-resistant reaction vessel had dropped sufficiently, the liquid temperature was lowered to 60 ° C., then 192 g of solid sodium hydroxide was added, and the liquid temperature was heated again to 120 ° C. Then, the pressure in the pressure resistant reactor was reduced for 3 hours to perform dehydration treatment, and the terminal hydroxyl group was replaced with -ONa.

Then, after returning the pressure to normal pressure with nitrogen gas, the liquid temperature was lowered to 100 ° C., and then 556 g of methyl chloride (1.1 equivalent to the theoretical hydroxyl terminal) was supplied over 2 hours. After feeding, it carried out aging for 2 hours the reaction was replaced with -ONa end to -OCH _3. Then, after removing unreacted methyl chloride, the product was taken out from the pressure resistant reactor.
3000 g of the obtained product was transferred to a 5 L separable flask, and 1000 g of distilled water and 25 g of phosphoric acid as a neutralizing agent for residual alkali were added. The separable flask was heated to 90 ° C., stirred, and neutralized for 1 hour. After confirming that the pH of the system was 7 or less, stirring was stopped. The resulting reaction solution was separated into two layers, and the upper aqueous layer containing neutralized salt (NaCl) was removed. Thereafter, 60 g of Kyowad 600S (magnesium silicate-based adsorbent) and 60 g of Kyowado 1000 (hydrotalcite-based adsorbent) (both manufactured by Kyowa Chemical Industry Co., Ltd.) were added as adsorbents for the neutralized salt remaining on the product side. Then, the mixture was heated to 120 ° C., stirred, subjected to adsorption treatment while degassing under reduced pressure for 2 hours, and then filtered to obtain the target polyoxyalkylene compound (Z-1). The obtained polyoxyalkylene compound (Z-1) had a polystyrene equivalent molecular weight (number average molecular weight Mn) of 700 and a weight average molecular weight of 742 as measured by GPC.

[Production Example 2: Production of polyoxyalkylene compound (Z-2)]
In Production Example 1, 670 g of dipropylene glycol was changed to 96 g of methanol, 2880 g of propylene oxide was changed to a mixture of 3180 g of propylene oxide and 324 g of ethylene oxide, the amount of sodium hydroxide used was changed from 192 g to 104 g, and methyl chloride Was changed from 556 g to 167 g. Other than that was carried out similarly to manufacture example 1, and obtained the target polyoxyalkylene compound (Z-2). The number average molecular weight Mn of the obtained polyoxyalkylene compound (Z-2) was 1200, and the weight average molecular weight was 1270.

[Production Example 3: Production of polyoxyalkylene compound (Z-3)]
Into a 5 L glass reaction vessel equipped with a stirring blade is charged 3000 g of polypropylene glycol (trade name: Exenol 1020, manufactured by Asahi Glass Co., Ltd.) and 224.4 g of acetic anhydride (2.2 equivalents relative to polypropylene glycol). , And reacted at 140 ° C. for 4 hours. After the reaction, reduced pressure treatment was performed at 140 ° C., and then 90 g of Kyowad 600S and Kyowad 1000 were added, and after adsorption treatment at 120 ° C. for 2 hours, filtration was performed to obtain the desired polyoxyalkylene compound (Z-3). . The obtained polyoxyalkylene compound (Z-3) had a polystyrene-reduced molecular weight (number average molecular weight Mn) of 1096 and a weight average molecular weight of 1160 as measured by GPC.

<Manufacture of polyether polyol>
<Initiator>
Initiator (1): Polyoxypropylene diol having a number average molecular weight (Mn) of 5,500 produced using a slurry catalyst (s).
Initiator (2): Polyoxypropylene diol having a number average molecular weight (Mn) of 10,000 produced using the slurry catalyst (s).
Initiator (3) :: Polyoxypropylene triol having a number average molecular weight (Mn) of 10,000 obtained by adding propylene oxide to glycerol using a slurry catalyst (s).

[Example 1]
The same pressure resistant reactor (capacity 5 L) as in Production Example 1 was used. First, in the pressure resistant reactor, 800 g of the initiator (1) and 800 g of the polyoxyalkylene compound (Z-2) produced in Production Example 2 (the ratio of the diluent to the total 100 parts by mass of the initiator and the total PO 25 Part by mass) and the slurry catalyst (s) produced in Reference Example 1 were added to prepare a reaction solution. The amount of the slurry catalyst (s) was 50 ppm as an amount converted to a DMC catalyst. Next, after replacing the inside of the pressure resistant reactor with nitrogen, the reaction solution was heated with stirring. When the temperature reached 130 ° C. (initial temperature), heating was stopped, and 80 g (10 parts by mass with respect to 100 parts by mass of the initiator) of PO was supplied into the pressure-resistant reaction vessel and allowed to react while continuing stirring.
In this example, the concentration of the slurry catalyst (s) is a concentration based on a total of 100 parts by mass of the initiator used for producing the polyether polyol and the total PO. The same applies to the following examples.

When PO was supplied into the pressure-resistant reaction vessel (start of the initial process), the internal pressure of the pressure-resistant reaction vessel once increased. Thereafter, the pressure gradually decreased, and it was confirmed that the pressure was the same as the internal pressure of the pressure-resistant reaction container immediately before supplying PO (end of the initial step). During this time, when the internal pressure began to decrease, the temperature of the reaction solution once increased, and then gradually decreased.
After completion of the initial process, 2320 g of PO was supplied into the pressure resistant reactor at 130 ° C. at a supply rate of 384 g / hour. It was confirmed that the internal pressure did not change and the reaction was completed.
The GPC spectrum of the polyether diol thus obtained showed a spectrum divided into two spectra: a spectrum due to the polyether diol and a spectrum due to the polyoxyalkylene compound (Z-2). The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn), hydroxyl value, and main production conditions of the spectrum derived from polyether diol are shown in Table 1 (the same applies hereinafter).
The hydroxyl value is a value (apparent hydroxyl value including polyoxyalkylene compound) measured by the above titration method (JIS K1557) for the obtained reaction product (including polyether diol and polyoxyalkylene compound). The values obtained by removing the amount corresponding to the polyoxyalkylene compound from the apparent hydroxyl value (hydroxyl value in terms of pure content) are shown in the table (the same applies hereinafter). Further, the viscosity of the reaction product was measured and shown in the table. In the table, “(Z)” or the like represents the polyoxyalkylene compound (Z).

[Examples 2 to 5, 17]
In Example 1, the type of initiator, the amount of initiator used, the type of polyoxyalkylene compound (Z), the amount of polyoxyalkylene compound (Z) used, the polyoxy to the total of 100 parts by mass of initiator and total PO The same procedure as in Example 1 except that the ratio of the alkylene compound (Z), the PO amount supplied in the initial step (PO for initial step), and the PO supply rate and supply amount in the polymerization step were changed as shown in Table 1. Thus, a polyether polyol was produced.
In any example, the amount of the slurry catalyst (s) used is 50 ppm, the amount of PO for the initial step is about 10 parts by weight with respect to 100 parts by weight of the initiator, and the initial step temperature and the polymerization step temperature are 130 ° C. .

[Comparative Example 1]
A polyether diol was produced in the same manner as in Example 1 except that the polyoxyalkylene compound (Z) was not used in Example 1. The viscosity was measured after the polyoxyalkylene compound (Z-2) was added to the obtained polyether diol so that the ratio was 20% by mass and mixed to be uniform.

[Comparative Example 2]
A polyether triol was produced in the same manner as in Example 4 except that the polyoxyalkylene compound (Z) was not used in Example 4. The viscosity was measured after the polyoxyalkylene compound (Z-2) was added to the obtained polyether triol so that the ratio thereof was 20% by mass and mixed uniformly.

[Comparative Example 3]
In Example 1, a polyether diol was produced in the same manner as in Example 1 except that 640 g of hexane as an organic solvent was used instead of 800 g of the polyoxyalkylene compound (Z-2). The viscosity was measured after hexane was removed by an evaporator, and then the polyoxyalkylene compound (Z-2) was added so that the ratio was 20% by mass and mixed to be uniform.

[Comparative Example 4]
A polyether diol was produced in the same manner as in Example 1, except that 900 g of tetrahydrofuran (THF) as an organic solvent was used instead of 800 g of the polyoxyalkylene compound (Z-2). The viscosity was measured after hexane was removed by an evaporator, and then the polyoxyalkylene compound (Z-2) was added so that the ratio was 20% by mass and mixed to be uniform.

As shown in the results of Table 1, the polyether polyols of Examples 1 to 5 and 17 produced using the specific polyoxyalkylene compound (Z) in the present invention have a high molecular weight and a molecular weight distribution. narrow.
On the other hand, in Example 1, Comparative Example 1 in which the polyoxyalkylene compound (Z) was not used, and Comparative Examples 3 and 4 in which an organic solvent was used instead of the polyoxyalkylene compound (Z) were both in Example 1. And the weight average molecular weight is almost the same, but the molecular weight distribution is wide.
In Example 4, Comparative Example 2 using an organic solvent instead of the polyoxyalkylene compound (Z) has a broad molecular weight distribution while the weight average molecular weight is almost the same as Example 4.

Production of a modified silicone polymer and production and evaluation of a modified silicone sealant will be described.
<Evaluation of tensile properties (H-type test)>
Surface anodized aluminum was used as the adherend, and an H-type test body was prepared in accordance with JIS A 1439 testing method for building sealing materials, and a tensile property test was performed.
Specifically, the prepared H-type specimen was cured at a temperature of 23 ° C. and a humidity of 65% for one week, and further cured at a temperature of 50 ° C. and a humidity of 65% for one week to prepare a cured product of the H-type specimen. . About the obtained hardened | cured material, a tensile physical property measurement (H-type physical property) is carried out with a Tensilon test machine, the stress (M50, unit: N / mm < ² >) when extended 50%, the maximum point tensile stress (unit: N) / Mm ² ) and maximum point elongation (unit:%) were measured.
The smaller the M50 value, the higher the flexibility, the higher the maximum point tensile stress value, the higher the tensile strength, and the higher the maximum point elongation value, the better the elongation.

<Manufacture of modified silicone polymer>
[Example 6: Production of modified silicone polymer (1)]
3,000 g of the polyether diol obtained in Example 2 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, while replacing the atmosphere in the reaction vessel with nitrogen gas and maintaining the internal temperature at 50 ° C., 10 ppm of dibutyltin diacetonate was added to the polyether diol as a urethanization catalyst, and after stirring, 3-Isocyanatopropyltrimethoxysilane (purity 97%) is added so that the ratio of the total number of isocyanate groups to the total number (NCO / OH) is 0.97. Subsequently, the internal temperature is maintained at 80 ° C. for 8 hours to cause urethanization reaction between polyether diol and 3-isocyanatopropyltrimethoxysilane, and the peak of isocyanate is observed by FT-IR (Fourier transform infrared spectroscopy). Confirm that it has disappeared. Then, it cools to normal temperature and the modified silicone polymer (1) which has a methyldimethoxysilyl group as a hydrolysable group at the terminal is obtained.

[Example 7: Production of modified silicone polymer (2)]
3,000 g of the polyether diol obtained in Example 2 was put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polyether diol was added, the methanol was removed by heating under reduced pressure, and the polyether was alcoholated. Thereafter, an excessive amount of allyl chloride was added to react with the amount of hydroxyl groups in the polyether diol, the unreacted allyl chloride was removed and purified, and a polymer having an allyl group at the molecular end was obtained. Next, in the presence of chloroplatinic acid hexahydrate, 0.85 moles of dimethoxymethylsilane was added to the terminal allyl group amount of the obtained polymer and reacted at 70 ° C. for 5 hours. . Thereby, a modified silicone polymer (2) having a methyldimethoxysilyl group as a hydrolyzable group at the terminal was obtained.

[Example 8: Production of modified silicone polymer (3)]
3,000 g of the polyether diol obtained in Example 3 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl groups of the polyether diol, the methanol is removed by heating under reduced pressure, and the polyether diol is alcoholated. Thereafter, an excessive amount of allyl chloride is added to react with the amount of hydroxyl groups in the polyether to cause reaction, and unreacted allyl chloride is removed and purified to obtain a polymer having an allyl group at the molecular end. Next, in the presence of chloroplatinic acid hexahydrate, 0.85 times moles of dimethoxymethylsilane is added to the terminal allyl group amount of the obtained polymer and reacted at 70 ° C. for 5 hours. Thereby, the modified silicone polymer (3) which has a methyldimethoxysilyl group as a hydrolysable group at the terminal is obtained.

[Example 9: Production of modified silicone polymer (4)]
3,000 g of the polyether diol obtained in Example 2 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl groups of the polyether diol, the methanol is removed by heating under reduced pressure, and the polyether diol is alcoholated. Thereafter, an excessive amount of allyl chloride is added to the amount of the hydroxyl group of the polyether diol to cause reaction, and unreacted allyl chloride is removed and purified to obtain a polymer having an allyl group at the molecular end. Next, in the presence of chloroplatinic acid hexahydrate, 0.85 moles of trimethoxyhydrosilane is added to the terminal allyl group amount of the obtained polymer, and the reaction is carried out at 70 ° C. for 5 hours. . As a result, a modified silicone polymer (4) having a trimethoxysilyl group as a hydrolyzable group at the terminal is obtained.

[Example 10: Production of modified silicone polymer (5)]
3,000 g of the polyether triol obtained in Example 5 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl group of the polyether triol is added, the methanol is removed by heating under reduced pressure, and the polyether triol is alcoholated. Thereafter, an excess amount of allyl chloride is added to the amount of the hydroxyl group of the polyether triol to cause reaction, and unreacted allyl chloride is removed and purified to obtain a polymer having an allyl group at the molecular end. Next, in the presence of chloroplatinic acid hexahydrate, 0.85 times moles of dimethoxymethylsilane is added to the terminal allyl group amount of the obtained polymer and reacted at 70 ° C. for 5 hours. Thereby, the modified silicone polymer (5) which has a methyldimethoxysilyl group as a hydrolysable group at the terminal is obtained.

[Example 11: Production and evaluation of sealing material]
100 parts by mass of the modified silicone polymer (1), 40 parts by mass of diisononyl phthalate (DINP, manufactured by Kao Corporation, trade name: Vinicizer 90), 75 parts by mass of colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Hakurei Hua CCR) , 75 parts by mass of heavy calcium carbonate (product name: Whiten SB, average particle size 1.78 μm), fatty acid amide type thixotropic agent (trade name: Disparon # 6500, manufactured by Enomoto Kasei Co., Ltd.) 5 parts by weight, 1 part by weight of benzotriazole UV absorber (Ciba Specialty Chemicals, trade name: Tinuvin 326), hindered phenol antioxidant (Ciba Specialty Chemicals, product) Name: 1 part by mass of Irganox 1010), tetravalent organotin compound (manufactured by Asahi Glass Co., Ltd .: EXCESTAR C201) 2 parts by mass are mixed to prepare a one-component modified silicone sealant. When the physical properties of the sealing material are measured, both the elongation physical properties and the strength are good. Moreover, workability at the time of construction is good even at room temperature and at a low temperature of 0 ° C.

[Examples 12 to 15]
In Example 11, the modified silicone polymer (1) is changed to the modified silicone polymers (2) to (5), respectively, and the sealing material is prepared in the same manner as in Example 11. When the physical properties of the obtained sealing material are measured, both the elongation physical properties and the strength are good. Moreover, workability at the time of construction is good even at room temperature and at a low temperature of 0 ° C.

[Example 16: Production of isocyanate group-terminated prepolymer]
400 g of the polyether diol obtained in Example 1 is put into a 1 L glass reaction vessel equipped with a stirring blade. In addition, tolylene diisocyanate (a mixture of 2,4-isomer and 2,6-isomer, containing 80% by mass of 2,4-isomer in a reaction tank. Trade name: TDI-80, manufactured by Nippon Polyurethane Industry Co., Ltd. ) And 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Millionate MT) at a molar ratio of 7/3 such that the isocyanate group / hydroxyl group (molar ratio) is 1.95 with respect to the polyether diol. Input only the amount. After replacing the inside of the reaction vessel with nitrogen, the reaction vessel is heated to 90 ° C. while stirring the content at 100 rpm, and maintained at 90 ° C. as it is. During the reaction, a part of the contents was taken out at regular intervals, and the isocyanate group content n ₁ (mass%) was measured. The isocyanate reaction rate n (% relative to the theoretical isocyanate group content n ₀ (mass%) was measured. ) The reaction is terminated after confirming that the isocyanate group content n ₁ (mass%) is less than or equal to the theoretical isocyanate group content z ₀ (0.84 mass%) to obtain an isocyanate group-terminated prepolymer. The obtained isocyanate group-terminated prepolymer is formed into a film having a thickness of about 200 μm on a release-treated PET film, cured at 25 ° C. for 7 days, and moisture-cured to obtain a cured product. When the physical properties of the obtained cured product are measured, both the elongation and the tensile strength at break are good.

<Manufacture of modified silicone polymer>
[Example 18: Production of modified silicone polymer (6)]
TDI used in this example is tolylene diisocyanate, and “TDI-80” means a mixture of 2,4-TDI / 2,6-TDI = 80/20 (mass ratio). 2EHA represents 2-ethylhexyl acrylate, and KBM903 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) is 3-aminopropyltrimethoxysilane. In advance, 184 g (1 mol) of 2EHA and 188 g (1.05 mol) of KBM903 were mixed at room temperature, and then allowed to stand at room temperature for 3 days to obtain a compound A (a compound having an —NH group and an —NH ₂ group). A mixture of compounds having
3,000 g of the polyether diol obtained in Example 2 was put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, the atmosphere in the reaction vessel is replaced with nitrogen gas, the temperature is lowered to 80 ° C., and 50 ppm of dibutyltin diacetonate is added to the polyether diol as a urethanization catalyst. TDI-80 (product name, manufactured by Nippon Polyurethane Co., Ltd.) was added and reacted for 7 hours to obtain an isocyanate-terminated prepolymer (p6). Subsequently, the atmosphere in the reaction vessel was replaced with nitrogen gas, and the prepolymer (p6) was cooled to 50 ° C.
Compound A is charged so that the ratio (NCO / NH) of the amino group of the synthesized product (A) calculated from the charged amount to the total number of isocyanate groups of the prepolymer (p6) is 1.05. did. Subsequently, the internal temperature is maintained at 80 ° C. for 8 hours under a nitrogen atmosphere, the prepolymer (p6) and the synthesized product A are reacted, and the peak of isocyanate is observed by FT-IR (Fourier transform infrared spectroscopy). Confirmed disappearance. Then, it cooled to normal temperature and obtained the modified silicone polymer (6) which has a trimethoxysilyl group as a hydrolysable group at the terminal.

<Manufacture of sealing agents>
[Example 19: Production and evaluation of sealing material]
143 parts by mass of the modified silicone polymer (6) of Example 18, 97 parts by mass of diisononyl phthalate (DINP, manufactured by Kao Corporation, trade name: Vinicizer 90), surface-treated calcium carbonate (trade name, manufactured by Shiraishi Calcium Co., Ltd.) as a filler : 110 parts by mass of white gloss flower CCR), 40 parts by mass of heavy calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Whiten SB, average particle size 1.78 μm), fatty acid amide type thixotropic agent (manufactured by Enomoto Kasei Co., Ltd.) , 3 parts by mass of trade name: Disparon # 6500), 1 part by mass of benzotriazole ultraviolet absorber (manufactured by Ciba Specialty Chemicals, trade name: Tinuvin 326), hindered phenol antioxidant (Ciba 1 part by mass of Specialty Chemical Co., Ltd., trade name: Irganox 1010), and a planetary stirrer It was stirred and mixed in a steel bow, Inc.). Next, after lowering the temperature to 25 ° C., 3 parts by mass of vinyltrimethoxysilane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical) 3 parts by weight of KBM-603) and 1 part by weight of 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) were added and mixed with stirring. Thereafter, 0.5 part by mass of dibutyltin dilaurate was added as a curing catalyst, and mixed by stirring to prepare a one-component modified silicone sealant. Table 2 shows the physical properties of the obtained sealing agent.
[Example 20: Production and evaluation of sealing material]
A one-component modified silicone sealant was prepared in the same manner as in Example 19 except that the modified silicone polymer (2) was used instead of the modified silicone polymer (6) in Example 19. Table 2 shows the physical properties of the obtained sealing material.

  As shown in Table 2, the sealing agent produced using the polyether polyol obtained by the production method of the present invention was good in both elongation properties and strength. The workability during construction was good even at room temperature and at a low temperature of 0 ° C.

The hydroxyl group-containing polyether obtained by the production method of the present invention includes a raw material of a synthetic resin such as a flexible polyurethane foam, a thermoplastic polyurethane resin or a thermosetting polyurethane resin, a raw material of a urethane prepolymer, a raw material of a modified silicone polymer, a surfactant. It can be widely used for lubricants and other applications.
The urethane prepolymer can be suitably used as an adhesive, a sealing agent, an adhesive, and a urethane waterproof material.
The modified silicone polymer can be suitably used as an adhesive, a sealing agent, and an adhesive.
The specification, claims and abstract of Japanese Patent Application No. 2012-247397 filed on November 9, 2012 and Japanese Patent Application No. 2012-288873 filed on Dec. 28, 2012 are as follows. The contents of which are hereby incorporated herein by reference.

Claims (15)

In the presence of the double metal cyanide complex catalyst and the following polyoxyalkylene compound (Z), a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator having at least one hydroxyl group per molecule, and the weight average molecular weight is 5,000. A process for producing a ~ 500,000 hydroxyl group-containing polyether,
The polyoxyalkylene compound (Z) is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction, and the weight average molecular weight of which is produced. A method for producing a hydroxyl group-containing polyether, which is a polyoxyalkylene compound smaller than the hydroxyl group-containing polyether.   The method for producing a hydroxyl group-containing polyether according to claim 1, wherein 10 to 300 parts by mass of the polyoxyalkylene compound (Z) is present with respect to 100 parts by mass of the hydroxyl group-containing polyether to be produced.   The method for producing a hydroxyl group-containing polyether according to claim 1 or 2, wherein the polyoxyalkylene compound (Z) is a polyoxyalkylene compound having an alkoxy group or an acyloxy group at the end of the polyoxyalkylene chain.   The method for producing a hydroxyl group-containing polyether according to claim 3, wherein the alkoxy group has 1 to 8 carbon atoms and the acyloxy group has 2 to 8 carbon atoms.   The hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1), wherein the polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and has 1 to 3 hydroxyl groups. The method for producing a hydroxyl group-containing polyether according to claim 3, which is a compound having a molecular weight per terminal group of 100 to 2,000, obtained by converting a group into an alkoxy group.   The method for producing a hydroxyl group-containing polyether according to any one of claims 3 to 5, wherein all of the terminal groups are methoxy groups.   The manufacturing method of the hydroxyl-containing polyether as described in any one of Claims 1-6 whose oxyalkylene group in the said polyoxyalkylene compound (Z) is an oxypropylene group. The hydroxyl group-containing polyether has a weight average molecular weight of 15,000 to 500,000,
The polyoxyalkylene compound (Z) has a hydroxyl group of a hydroxyl group-containing polyoxyalkylene compound (z1) having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups. A polyoxyalkylene compound having a molecular weight of 100 to 1000 per end group, obtained by conversion to an alkoxy group,
The manufacturing method of the hydroxyl-containing polyether of Claim 1 which makes the said polyoxyalkylene compound (Z) exist 10-80 mass parts with respect to 100 mass parts of hydroxyl-containing polyether manufactured.   The method for producing a hydroxyl group-containing polyether according to claim 8, wherein the alkoxy group has 1 to 4 carbon atoms.   The method for producing a hydroxyl group-containing polyether according to claim 8 or 9, wherein all of the terminal groups are methoxy groups.   The manufacturing method of the hydroxyl-containing polyether as described in any one of Claims 8-10 whose oxyalkylene group in the said polyoxyalkylene compound (Z) is an oxypropylene group. A step of producing a hydroxyl group-containing polyether by the production method according to any one of claims 1 to 11,
A method for producing a hydrolyzable silyl group-containing polyether, comprising a step of reacting a hydroxyl group of the obtained hydroxyl group-containing polyether with a hydrolyzable silyl group-containing compound.   The method for producing a hydrolyzable silyl group-containing polyether according to claim 12, wherein the hydrolyzable silyl group-containing compound is a compound having an isocyanate group and a hydrolyzable silyl group. A step of producing a hydroxyl group-containing polyether by the production method according to any one of claims 1 to 11,
The manufacturing method of the urethane prepolymer which has the process of making a polyisocyanate compound react with the obtained hydroxyl-containing polyether.   Hydrolyzable silyl group-containing, characterized in that the urethane prepolymer obtained in claim 14 is reacted with a compound having an active hydrogen-containing group capable of reacting with an isocyanate group and a hydrolyzable silyl group. A method for producing a polyether.