JP2024108098A - Polyether polyol - Google Patents

Abstract

[Problem] The objective of the present invention is to provide a polyether polyol that has excellent compatibility with urethane raw materials, good reactivity as a urethane raw material, and is capable of exhibiting excellent tensile resistance when made into polyurethane. [Solution] A polyether polyol represented by the following formula (1), in which the ratio of the amount of oxymethylene groups present in bond to each other to the total amount of oxymethylene groups is 8.0% or less, and the molecular weight distribution is 1.85 or more. TIFF2024108098000005.tif30155 (In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer from 1 to 40, m is an integer of 1 or more, and s is an integer from 1 to 30. Note that in formula (1), multiple Rs may be the same or different.) [Selected Figure] None

Description

The present invention relates to a polyether polyol, and more particularly to a polyether polyol having an oxymethylene structure in the main chain.

Polyether polyols are polyether polyols having primary hydroxyl groups at both ends and represented by the general formula HO-(RO)m-H (m is an integer of 2 or more, and R is an alkylene group), and are generally produced by ring-opening polymerization of cyclic ethers. Among them, tetrahydrofuran (
Polytetramethylene ether glycol (hereinafter sometimes abbreviated as "PTMG") obtained by the ring-opening polymerization reaction of tetramethylphenyl ether (THF) is a linear polyether glycol having hydroxyl groups at both ends and is represented by the general formula HO-[( _CH2 ) _4O ]n-H (n is an integer of 2 or more), and is extremely useful as a raw material for polyurethanes and polyesters, which require elasticity and flexibility.

In recent years, in fields requiring polyurethanes and polyesters with high elastic modulus and high strength, the use of high molecular weight PTMG and the like is desired. However, high molecular weight PTMG and the like have high viscosity and are inconvenient to handle, but the viscosity has been reduced by introducing an oxymethylene group into the PTMG. Patent Document 1 describes a method for producing a PTMG having a number average molecular weight of 650 to 3000, or a PTMG and glycol having a number average molecular weight of 650 to 3000,
PTMG is made by using paraformaldehyde or formaldehyde as a raw material, and refining it by steam distillation in the presence of calcium hydroxide using a solid acid catalyst such as montmorillonite.
describes a method for producing a polyol having an oxymethylene group introduced therein.

Patent Document 2 describes a polyol having a number average molecular weight of 2000 to 13000, which is produced by using PTMG having a number average molecular weight of 1000 to 3000 and paraformaldehyde or formaldehyde as raw materials, introducing an oxymethylene group into PTMG using a solid acid catalyst such as Amberlyst at a temperature of 60° C. to 110° C.

Patent Document 3 describes the production of a polyether polyol having a number average molecular weight of at least 1270, the number of hydroxyl groups of less than 200, and an oxymethylene structure, using an alkylene diol such as pentanediol or a polyol such as PTMG and paraformaldehyde as raw materials and an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid at a temperature not exceeding 130°C.

Special Publication No. 7-505176 Japanese Unexamined Patent Publication No. 57-53529 British Patent No. 850178

However, when a polyurethane is produced using a previously known polyether polyol having an oxymethylene structure as a raw material, the tensile strength and elongation at break of the produced polyurethane are unsatisfactory and insufficient.

The present invention has been made in consideration of the above problems, and has an object to provide a polyether polyol that has excellent compatibility with urethane raw materials, has good reactivity as a urethane raw material, and is capable of exhibiting excellent tensile resistance when made into a polyurethane.

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by providing a polyether polyol in which the ratio of the amount of oxymethylene groups present in bond to each other to the total amount of oxymethylene groups in a specific polyether polyol is within a specific range, and the molecular weight distribution is within a specific range, thereby completing the present invention.
That is, the gist of the present invention lies in the following [1] and [2].
[1] A polyether polyol represented by the following formula (1), in which the ratio of the amount of oxymethylene groups present in bond to each other to the total amount of oxymethylene groups is 8.0% or less, and the molecular weight distribution is 1.85 or more.

In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n represents an integer of 1 to 40.
where m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple Rs may be the same or different.
[2] The number average molecular weight of the polyether polyol is 600 or more and 9900 or less.
1. The polyether polyol according to claim 1.

According to the present invention, it is possible to provide a polyether polyol that has excellent compatibility with urethane raw materials, has good reactivity as a urethane raw material, and is capable of exhibiting excellent tensile resistance when made into a polyurethane.

The present invention will be described in detail below, but the present invention is not limited to the embodiments described below as long as it does not depart from the gist of the present invention.

<Polyether polyol>
The polyether polyol of the present invention is a polyol represented by the following formula (1), in which the ratio of the amount of oxymethylene groups present by bonding to each other to the total amount of oxymethylene groups (hereinafter sometimes referred to as the "oxymethylene continuous bond ratio") is 8.0% or less and the molecular weight distribution is 1.85 or more (hereinafter referred to as "polyether polyol A").
(sometimes referred to as "the

In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n represents an integer of 1 to 40.
where m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple Rs may be the same or different.

The proportion of continuous oxymethylene bonds in the polyether polyol A is preferably 5.0% or less,
It is more preferably 3.0% or less, and even more preferably 2.0% or less. The lower limit is not particularly limited, but 0.1% is preferable. By setting the oxymethylene continuous bond ratio within the above range, it is possible to provide a polyether polyol that has excellent compatibility with urethane raw materials when polyether polyol A is used as a urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into polyurethane.
The proportion of consecutive oxymethylene bonds can be determined by ¹ H-NMR measurement (proton nuclear magnetic resonance spectroscopy).

The molecular weight distribution of polyether polyol A is preferably 1.90 or more, more preferably 2.00 or more, and even more preferably 2.30 or more. The upper limit is not particularly limited, but is preferably 3.50, and more preferably 3.20. By making the molecular weight distribution within the above range, when polyether polyol A is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into polyurethane.
The molecular weight distribution can be measured by GPC (gel permeation chromatography).

The number average molecular weight of the polyether polyol A is preferably from 600 to 9900, more preferably from 800 to 5900, and even more preferably from 1000 to 3900. By setting the number average molecular weight within the above range, it is possible to provide a polyether polyol that, when used as a urethane raw material, has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into a polyurethane.
The number average molecular weight can be measured by GPC (gel permeation chromatography).

In the formula (1), R is preferably a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, and more preferably a divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms, because it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material when polyether polyol A is used as a urethane raw material, has good reactivity as a urethane raw material, and exhibits excellent tensile resistance when made into a polyurethane. Examples of the divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2
a hydrocarbon group derived from a linear polyol such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, or 1,10-decanediol;
Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,4-butanediol, 3-methyl-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-
Propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,
Examples of the hydrocarbon groups include those derived from branched polyols such as 1,3-propanediol and 1,2-dibutyl-5-pentanediol.
More preferred are hydrocarbon groups derived from at least one polyol selected from the group consisting of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.

Examples of the divalent cyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms include 1,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, isosorbide, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, 1,3
-Cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.
1.0 ^2,6 ] decanedimethanol, etc. Among these, a hydrocarbon group derived from at least one polyol selected from the group consisting of erythritan, isosorbide, and 1,4-cyclohexanedimethanol is more preferred.

(Production of Polyether Polyol A)
<Raw Material 1>
The raw material for producing the polyether polyol of the present invention includes the raw material that is the basis of the formula (1). The raw material that is the basis is at least one compound selected from the group consisting of formaldehyde, paraformaldehyde, and trioxane (hereinafter, sometimes referred to as "raw material 1"). Formaldehyde is generally used as an aqueous solution as formalin, and when formaldehyde is used as a raw material, it is necessary to remove a large amount of water from the reaction system for polyether polyol purification. Therefore, trioxane and paraformaldehyde are preferred as raw material 1, and paraformaldehyde is more preferred, because they can efficiently produce polyether polyol.

The amount of raw material 1 is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and even more preferably 1% by mass or more and 25% by mass or less, based on the total amount of the raw materials.

<Raw material 2>
The raw material includes, in addition to raw material 1, a polyol other than raw material 1 (hereinafter, sometimes referred to as “raw material 2”). Raw material 2 is a polyether polyol other than raw material 1 and/or a polyol other than raw material 1.

As the polyether polyol other than raw material 1 (hereinafter sometimes referred to as "raw material 2-1"), aliphatic polyether polyols are preferred, and non-cyclic aliphatic polyether polyols are more preferred, because when polyether polyol A is used as a urethane raw material, a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into polyurethane can be provided. Examples of non-cyclic aliphatic polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, copolymerized polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, copolymerized polyether polyol of neopentyl glycol and tetrahydrofuran, copolymerized polyether polyol of ethylene oxide and tetrahydrofuran, and copolymerized polyether glycol of propylene oxide and tetrahydrofuran. Among them, polytetramethylene ether glycol is more preferred. Examples of cyclic aliphatic polyether polyols include 1,
3-Cyclopentanediol, 1,4-Cyclohexanediol, Erythritan, 1,4
and polyether polyols obtained by polymerizing at least one polyol selected from the group consisting of 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, and tricyclo[5.2.1.0 ^2,6 ]decane dimethanol. Among these, polyether polyols obtained by polymerizing 1,4-cyclohexanedimethanol are more preferred.

The number average molecular weight of raw material 2-1 is preferably from 100 to 4000, more preferably from 150 to 1000, and even more preferably from 200 to 900. When polyether polyol A is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into polyurethane.

As the polyol other than raw material 1 (hereinafter sometimes referred to as "raw material 2-2"), when polyether polyol A is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when made into polyurethane. Therefore, an acyclic aliphatic polyol is preferable, and an acyclic aliphatic polyol is more preferable. Examples of the acyclic aliphatic polyol include ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,4-butanediol, 3-methyl-
Pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,
Examples of the cyclic aliphatic polyol include 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, and 2,2-dibutyl-1,3-propanediol. Among them, at least one polyol selected from the group consisting of 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is more preferred.
,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, isosorbide, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.1.02,6]decanedimethanol, and the like.
More preferred is at least one polyol selected from the group consisting of erythritan, isosorbide and 1,4-cyclohexanedimethanol.

Incidentally, it is preferable that raw material 2 contains raw material 2-1, since this allows efficient production of a polyether polyol having a desired number average molecular weight.

<Catalyst>
The catalyst for producing the polyether polyol A used in the present invention is preferably an acidic ion exchange resin catalyst, more preferably an acidic ion exchange resin catalyst having a sulfonic acid group. By using the catalyst, it becomes possible to control the ratio of continuous oxymethylene bonds in the produced polyether polyol A within a specific range.

The amount of the catalyst is preferably 0.1% by weight to 10% by weight, more preferably 0.5% by weight to 5% by weight, and even more preferably 1% by weight to 3% by weight, based on the weight of the raw material 2. By using the amount of the catalyst within the above range, it is possible to suppress acid decomposition of the raw material 2 and to control the ratio of continuous oxymethylene bonds in the produced polyether polyol A within a specific range.

<Reaction process>
The reaction of producing polyether polyol A using raw materials 1 and 2 as raw materials in the presence of a catalyst is carried out in the following reaction system. The reaction system may be a batch system or a continuous system, but the batch system is preferred because it is easy to remove water by-produced in the reaction system. If necessary, a solvent that does not affect the reaction may be present in the reaction system. Examples of the solvent include tetrahydrofuran, cyclopentyl methyl ether, benzene, toluene, xylene, cyclohexane, etc., but toluene, xylene, and cyclohexane are preferred from the viewpoint of stability against the catalyst.

The reaction starts when the raw material 1, raw material 2, and the catalyst are present in the reaction system. The reaction temperature is preferably 60° C. or higher and 130° C. or lower, more preferably 70° C. or higher and 120° C. or lower, and more preferably 90° C. or higher.
The reaction temperature is preferably in the range of 100° C. or more and 110° C. or less. By setting the reaction temperature in the above range, the water generated in the reaction system can be easily removed from the system even under normal pressure. The reaction pressure is preferably 50 kPa or less.
Preferably, the pressure is 1000 kPa or more, and more preferably, the pressure is 70 kPa or more and 500 kPa or less.
The reaction pressure is more preferably from 90 kPa to 150 kPa. By setting the reaction pressure in this range, it is possible to retain the raw material within the reaction system and to efficiently remove moisture.

After a suitable time has elapsed since the start of the reaction, a catalyst deactivator such as magnesium hydroxide, aluminum oxide, or hydrotalcite may be added to the reaction system, taking into consideration the number average molecular weight of the desired polyether polyol A, to deactivate trace amounts of acidic impurities remaining in the system. The deactivator may also be removed. The method for removing the deactivator may include filtration or the like.

When it is confirmed that the raw material 1 has been consumed, i.e., the reaction has ended, the catalyst is removed from the reaction system by filtration or the like. After that, the solvent and water are removed from the reaction system.
The temperature is preferably 0° C. or higher and 180° C. or lower, more preferably 90° C. or higher and 160° C. or lower, and even more preferably 100° C. or higher and 150° C. or lower. By setting the temperature within the above range, the water and solvent generated during the reaction can be efficiently removed from the reaction system. The pressure is preferably 1 Pa or higher and 50 kPa or lower, more preferably 10 Pa or higher and 10 kPa or lower, and even more preferably 50 Pa or higher and 1 kPa or lower. By setting the pressure within the above range, the solvent and water may be efficiently removed.

After removing the solvent and water, heating is continued under reduced pressure as necessary. The temperature is preferably 100° C. or higher, more preferably 130° C. or higher, in terms of promoting depolymerization, which will be described later.
More preferably, the reaction temperature is 140°C or higher. In order to prevent the decomposition of the product, the reaction temperature is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. By setting the reaction temperature within the above range, it is possible to depolymerize the sites in which oxymethylene groups in polyether polyol A are continuously bonded, and to rearrange them into a structure in which structural units derived from raw material 2 and oxymethylene groups are alternately bonded, making it possible to set the ratio of continuous oxymethylene bonds within a specific range. In addition, the reaction pressure is set to 0.5 to 1000°C in order to remove the remaining unreacted raw materials 1 and 2 from the reaction system.
The pressure is preferably from 1 kPa to 500 kPa, more preferably from 0.5 kPa to 100 kPa, and even more preferably from 1 kPa to 10 kPa.

[Uses of polyether polyol]
The polyether polyol of the present invention is useful as a raw material for polyurethane suitable for applications such as elastic fiber, thermoplastic polyurethane, and coating material due to its excellent reactivity and tensile resistance. In such applications, a polyurethane solution or an aqueous polyurethane emulsion can be produced from the polyether polyol of the present invention and used. The polyether polyol of the present invention can be used as a raw material for UV-curable paints, electron beam-curable paints, plastic coatings, molding agents for lenses, sealants, adhesives, etc. by modifying the terminals. The polyether polyol of the present invention can be used to disperse nanomaterials such as nanofiber cellulose, carbon nanofibers, and metal nanoparticles.

[Polyurethane]
The polyether polyols of the present invention can be used to produce polyurethanes.
In the method for producing polyurethane using the polyether polyol of the present invention, known polyurethane-forming reaction conditions for producing ordinary polyurethanes are used.

For example, polyurethane can be produced by reacting the polyether polyol of the present invention with a polyisocyanate and a chain extender at a temperature in the range of from room temperature to 200°C.
Alternatively, the polyether polyol of the present invention can be reacted with an excess of polyisocyanate to produce a prepolymer having an isocyanate group at its terminal, and then a chain extender can be used to increase the degree of polymerization to produce a polyurethane.

<Polyisocyanate>
The polyisocyanate used in producing a polyurethane using the polyether polyol of the present invention may be any of various known aliphatic, alicyclic or aromatic polyisocyanate compounds.
For example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted to isocyanate groups; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2
alicyclic diisocyanates such as 1,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane; xylylene diisocyanate, 4,4'-diphenyl diisocyanate, and 2,4-tolylene diisocyanate;
Examples of the aromatic diisocyanates include 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred in that they give polyurethanes with a good balance of physical properties and are available industrially in large quantities at low cost.

<Chain extender>
The chain extender used in producing polyurethane is a low molecular weight compound having at least two active hydrogens that react with isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later. Typical examples of the chain extender include polyols and polyamines.

Specific examples thereof include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2
diols having a branched chain, such as dimer diol and diethyl ether group; diols having an ether group, such as diethylene glycol and propylene glycol;
, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane and other diols having an alicyclic structure, xylylene glycol,
Examples of the polyols include glycerin, trimethylolpropane, pentaerythritol, and other polyols; N-methylethanolamine, N-ethylethanolamine, and other hydroxyamines; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine, and other polyamines; and water.

These chain extenders may be used alone or in combination of two or more of them. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,2-butanediol are preferred in terms of the favorable balance of physical properties of the resulting polyurethane and the fact that they are available in large quantities industrially at low cost.
1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4'-diaminodicyclohexylmethane are preferred.
Furthermore, the chain extender used in producing a prepolymer having a hydroxyl group, which will be described later, is a low molecular weight compound having at least two isocyanate groups, and specific examples thereof include the compounds described in the <Polyisocyanate> section.

<Chain Terminator>
When producing the polyurethane, a chain terminator having one active hydrogen group can be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane.
Examples of these chain terminators include aliphatic monools having one hydroxyl group, such as methanol, ethanol, propanol, butanol, and hexanol, and aliphatic monoamines having one amino group, such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine, and morpholine.
These may be used alone or in combination of two or more.

<Catalyst>
In the polyurethane-forming reaction for producing polyurethane, triethylamine, N-
Amine catalysts such as ethylmorpholine and triethylenediamine, or acetic acid, phosphoric acid, sulfuric acid,
It is also possible to use known urethane polymerization catalysts, such as acid catalysts such as hydrochloric acid and sulfonic acid, tin compounds such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecane, and organometallic salts such as titanium compounds. The urethane polymerization catalysts may be used alone or in combination of two or more.

<Polyols other than the polyether polyol of the present invention>
In the polyurethane-forming reaction for producing polyurethane, the polyether polyol of the present invention may be used in combination with other polyols as necessary. Here, the polyol other than the polyether polyol of the present invention is not particularly limited as long as it is one that is used in normal polyurethane production, and examples thereof include polyether polyols, polyester polyols, polycaprolactone polyols, and polycarbonate polyols other than the polyether polyol of the present invention.
Here, the weight ratio of the polyether polyol of the present invention to the total weight of the polyether polyol of the present invention and the other polyols is preferably 70% or more, more preferably 90% or more. If the weight ratio of the polyether polyol of the present invention is small, the compatibility between the polyurethane raw materials, which is a feature of the present invention, and the strength and handleability of the polyurethane may be lost.

For the production of polyurethane, the polyether polyol of the present invention may be modified and used. Methods for modifying polyether polyol include a method of adding an epoxy compound such as ethylene oxide, propylene oxide, or butylene oxide to a polyether polyol to introduce an ether group, and a method of reacting a polyether polyol with a cyclic lactone such as ε-caprolactone, a dicarboxylic acid compound such as adipic acid, succinic acid, sebacic acid, or terephthalic acid, or an ester compound thereof to introduce an ester group.

In the case of ether modification, modification with ethylene oxide, propylene oxide, etc. reduces the viscosity of the polyol, which is preferable for reasons of handling and the like. In addition, since the polyether polyol of the present invention has high tensile resistance, it is possible to maintain high tensile strength, which is usually reduced by modification with ethylene oxide or propylene oxide. Furthermore, in the case of ethylene oxide modification, the water absorption and moisture permeability of the polyurethane produced using the ethylene oxide modified polyether polyol are increased, so that the performance as artificial leather, synthetic leather, etc. may be improved. The amount of ethylene oxide or propylene oxide added to the polyether polyol is preferably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight, from the viewpoints of mechanical strength, heat resistance, chemical resistance, etc.

The method of introducing an ester group is preferable because the viscosity of the polyether polyol is reduced by modification with ε-caprolactone, and this is advantageous for reasons of ease of handling, etc.
The amount of -caprolactone added is suitably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight, from the viewpoint of the hydrolysis resistance, chemical resistance, tensile resistance, etc. of the resulting polyurethane.

<Solvent>
A solvent may be used in the polyurethane-forming reaction when producing the polyurethane.
Preferred solvents include amide-based solvents such as dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone, sulfoxide-based solvents such as dimethylsulfoxide, tonne-based solvents such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone, ether-based solvents such as tetrahydrofuran and dioxane, ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate, and aromatic hydrocarbon-based solvents such as toluene and xylene. These solvents may be used alone or as a mixed solvent of two or more of them.

Among these, preferred organic solvents are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and the like.
Moreover, a polyurethane in the form of a water dispersion can also be produced from a polyurethane composition containing the polyether polyol of the present invention, a polyisocyanate, and the above-mentioned chain extender.

<Polyurethane manufacturing method>
As a method for producing polyurethane using the above-mentioned reactants, a production method generally used in experiments or industrially can be used.
Examples of such a method include a method in which the polyether polyol of the present invention, other polyols, polyisocyanate, and chain extender are mixed together and reacted (hereinafter, sometimes referred to as a "single-stage method"), and a method in which the polyether polyol of the present invention, other polyols, and polyisocyanate are first reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer is reacted with a chain extender (hereinafter, sometimes referred to as a "two-stage method").

The two-stage method involves a step of preparing an intermediate having isocyanates at both ends of the part corresponding to the soft segment of polyurethane by reacting the polyether polyol of the present invention and another polyol with one equivalent or more of polyisocyanate in advance. In this way, if a prepolymer is prepared and then reacted with a chain extender, it may be easy to adjust the molecular weight of the soft segment part, and this is useful when it is necessary to ensure phase separation of the soft segment and the hard segment.

<One-step method>
The one-stage method, also called the one-shot method, is a method in which the polyether polyol of the present invention, other polyol, polyisocyanate and chain extender are charged all at once to carry out the reaction.
The amount of polyisocyanate used in the one-stage process is not particularly limited, but when the total number of hydroxyl groups in the polyether polyol of the present invention and the other polyol and the sum of the number of hydroxyl groups and the number of amino groups in the chain extender is taken as 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, even more preferably 0.9 equivalents, and particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, even more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

When the amount of polyisocyanate used is equal to or greater than the lower limit, the molecular weight of the polyurethane becomes sufficiently large, resulting in good polyurethane strength. When the amount of polyisocyanate used is equal to or less than the upper limit, side reactions due to unreacted isocyanate groups are suppressed, resulting in good handleability and flexibility of the resulting polyurethane solution.
The amount of the chain extender used is not particularly limited, but when the total number of hydroxyl groups in the polyether polyol of the present invention and other polyols is subtracted from the number of isocyanate groups in the polyisocyanate, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents.
More preferably, it is 0.9 equivalents, and particularly preferably, it is 0.95 equivalents. The upper limit is preferably 3
0 equivalents, more preferably 2.0 equivalents, even more preferably 1.5 equivalents, and particularly preferably 1.
If the amount of chain extender used is equal to or more than the lower limit, the strength of the resulting polyurethane is improved.
The hardness, heat resistance, elastic recovery performance and elasticity retention performance become good, and if it is not more than the upper limit, the processability of the obtained polyurethane becomes good.

<Two-step method>
The two-stage method is also called the prepolymer method, and mainly includes the following methods.
(a) A method in which the polyether polyol of the present invention and the other polyol are reacted in advance with an excess of polyisocyanate at a reaction equivalent ratio of polyisocyanate/(the polyether polyol of the present invention and the other polyol) of from more than 1 to 10.0 or less to produce a prepolymer having isocyanate groups at the molecular chain terminals, and then a chain extender is added to the prepolymer to produce a polyurethane.
(b) A method in which a polyisocyanate is reacted in advance with an excess of a polyether polyol and another polyol at a reaction equivalent ratio of polyisocyanate/(the polyether polyol of the present invention and the other polyol) of 0.1 or more and less than 1.0 to produce a prepolymer having hydroxyl groups at the molecular chain ends, and then a polyisocyanate having isocyanate groups at its terminals as a chain extender is reacted with this to produce a polyurethane.

The two-stage process can be carried out in the absence of a solvent or in the presence of a solvent.
The two-stage polyurethane production can be carried out by any of the following methods (1) to (3).
(1) Without using a solvent, a polyisocyanate is first reacted directly with a polyether polyol and another polyol to synthesize a prepolymer, which is then used as is in the chain extension reaction.
(2) A prepolymer is synthesized by the method in (1), then dissolved in a solvent and used in the subsequent chain extension reaction.
(3) A solvent is used from the beginning, polyisocyanate, polyether polyol, and other polyol are reacted, and then a chain extension reaction is carried out.

In the case of method (1), it is important to obtain the polyurethane in the coexistence with the solvent in the chain extension reaction by, for example, dissolving the chain extender in the solvent or dissolving the prepolymer and the chain extender simultaneously in the solvent.
The amount of polyisocyanate used in the two-stage process (a) is not particularly limited, but may be
The lower limit of the number of isocyanate groups when the total number of hydroxyl groups of the polyether polyol and the other polyols is taken as 1 equivalent is preferably an amount exceeding 1.0 equivalent, more preferably 1.
The amount of the carboxylic acid is preferably 0.2 equivalents, more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, and even more preferably 3.0 equivalents.

When the amount of polyisocyanate used is equal to or greater than the lower limit, the molecular weight of the resulting polyurethane will be sufficiently large, and the strength and thermal stability will be good. When the amount is equal to or less than the upper limit, side reactions due to excess isocyanate groups can be suppressed, and the handleability and flexibility of the resulting urethane will be good.
The amount of the chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and even more preferably 0.8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, based on 1 equivalent of the number of isocyanate groups contained in the prepolymer.
0 equivalents, and more preferably 2.0 equivalents.

When the chain extension reaction is carried out, monofunctional organic amines or alcohols may be allowed to coexist for the purpose of adjusting the molecular weight.
The amount of polyisocyanate used in preparing a prepolymer having a hydroxyl group at the end in the two-stage process (b) is not particularly limited, but the lower limit of the number of isocyanate groups when the total number of hydroxyl groups in the polyether polyol and the other polyols is taken as 1 equivalent is preferably 0.1 equivalent, more preferably 0.5 equivalent, and even more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0.98 equivalent, and even more preferably 0.
.97 equivalents.

If the amount of polyisocyanate used is equal to or greater than the lower limit, the process for obtaining the desired molecular weight by the subsequent chain extension reaction can be shortened, resulting in good production efficiency, whereas if it is equal to or less than the upper limit, the handleability and flexibility of the resulting polyurethane will be good.
The amount of the chain extender used is not particularly limited. When the total number of hydroxyl groups of the polyether polyol and other polyols used in the prepolymer is taken as 1 equivalent, the total equivalent including the equivalent of the isocyanate group used in the prepolymer is preferably 0.7 equivalents at the lower limit, more preferably 0.8 equivalents, and even more preferably 0.9 equivalents at the upper limit.
The amount is preferably less than 0.0 equivalents, more preferably 0.99 equivalents, and even more preferably 0.98 equivalents.

When the chain extension reaction is carried out, monofunctional organic amines or alcohols may be allowed to coexist for the purpose of adjusting the molecular weight.
The chain extension reaction is usually carried out at 0°C to 250°C, but this temperature varies depending on the amount of solvent, the reactivity of the raw materials used, the reaction equipment, etc., and is not particularly limited. If the temperature is too low, the reaction will proceed slowly, or the production time may be long due to the low solubility of the raw materials and polymers, while if the temperature is too high, side reactions or decomposition of the resulting polyurethane may occur. The chain extension reaction may be carried out under reduced pressure while degassing.

In addition, a catalyst, a stabilizer, etc. may be added to the chain extension reaction, if necessary.
Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate,
Examples of the stabilizer include compounds such as stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one type may be used alone or two or more types may be used in combination. Examples of the stabilizer include compounds such as 2,6-dibutyl-4-methylphenol, distearyl thiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, and tris(dinonylphenyl)phosphite, and one type may be used alone or two or more types may be used in combination. When the chain extender is a highly reactive one such as a short-chain aliphatic amine, the process may be carried out without adding a catalyst.

<Water-based polyurethane emulsion>
When an aqueous polyurethane emulsion is produced using the polyether polyol of the present invention, a polyol containing the polyether polyol of the present invention is reacted with an excess of polyisocyanate to produce a prepolymer, and the polyol has at least one hydrophilic functional group and at least two hydrophilic functional groups.
A compound having an isocyanate-reactive group is mixed to form a prepolymer, which is then subjected to a neutralization salt process for the hydrophilic functional groups, an emulsification process by adding water, and a chain extension reaction process to produce an aqueous polyurethane emulsion.

The hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used herein is, for example, a carboxyl group or a sulfonic acid group, which is a group that can be neutralized with an alkaline group. The isocyanate-reactive group is a group that generally reacts with isocyanate to form a urethane bond or a urea bond, such as a hydroxyl group, a primary amino group, or a secondary amino group, and these may be mixed in the same molecule.

Specific examples of compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2'-dimethylolpropionic acid, 2,2-methylolbutyric acid, 2,2'-dimethylolvaleric acid, etc. Also included are diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid, etc. These include:
One type may be used alone, or two or more types may be used in combination. When these are actually used, they may be neutralized with an amine such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, or triethanolamine, or an alkaline compound such as sodium hydroxide, potassium hydroxide, or ammonia.

In producing a water-based polyurethane emulsion, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is preferably 1% by weight, more preferably 5% by weight, and even more preferably 10% by weight based on the total weight of the polyether polyol of the present invention and other polyols in order to improve the dispersibility in water, while the upper limit is preferably 50% by weight, more preferably 40% by weight, and even more preferably 30% by weight in order to maintain the properties of the polyether polyol.

When producing an aqueous polyurethane emulsion, the reaction may be carried out in the prepolymer step in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone, or may be carried out without a solvent. When a solvent is used, it is preferable to remove the solvent by distillation after producing the aqueous emulsion.

When producing an aqueous polyurethane emulsion without solvent using the polyether polyol of the present invention as a raw material, the upper limit of the number average molecular weight calculated from the hydroxyl value of the polyether polyol used is preferably 5000, more preferably 4500, and even more preferably 4000. The lower limit of the number average molecular weight of the polyether polyol is preferably 300, more preferably 500, and even more preferably 800. If the number average molecular weight calculated from the hydroxyl value is within the above range, emulsification tends to be easy.

In addition, during synthesis or storage of the aqueous polyurethane emulsion, emulsion stability may be maintained by using in combination an anionic surfactant, such as a higher fatty acid, a resin acid, an acidic fatty alcohol, a sulfate ester, a higher alkyl sulfonate, an alkylaryl sulfonate, a sulfonated castor oil, or a sulfosuccinate; a cationic surfactant, such as a primary amine salt, a secondary amine salt, a tertiary amine salt, a quaternary amine salt, or a pyridinium salt; or a nonionic surfactant, such as a known reaction product of ethylene oxide with a long-chain fatty alcohol or a phenol.

In addition, when preparing a water-based polyurethane emulsion, the emulsion can also be produced by mechanically mixing water with an organic solvent solution of the prepolymer under high shear in the presence of an emulsifier, if necessary, without the neutralization/salting step.
The water-based polyurethane emulsions produced in this way can be used for a variety of purposes. In particular, in light of the recent demand for chemical raw materials with a low environmental impact, they can be used as a replacement for conventional products that do not use organic solvents.

Specific applications of the aqueous polyurethane emulsion include, for example, coating agents, aqueous paints, adhesives, synthetic leather, and artificial leather. In particular, the aqueous polyurethane emulsion produced using the polyether polyol of the present invention has excellent tensile resistance due to the polyether polyol, and can be used more effectively as a coating agent than conventional aqueous polyurethane emulsions using polycarbonate diol or PTMG. In particular, compared to conventional aqueous polyurethane emulsions using PTMG, the aqueous polyurethane emulsion has a hydrophilic group, so it has good affinity with water and can use the polyether polyol of the present invention with a higher molecular weight, so that it can impart softness and transparency to coating films, synthetic leather, artificial leather, etc. In addition, since the aqueous polyurethane emulsion has excellent dispersibility in water, the degree of freedom in molecular design of the aqueous polyurethane emulsion is increased, and it is possible to produce a matte texture by adjusting the composition.

The storage stability of the polyurethane solution and aqueous polyurethane emulsion produced using the polyether polyol of the present invention using an organic solvent and/or water can be measured by adjusting the polyurethane concentration in the solution or emulsion (hereinafter sometimes referred to as "solids concentration") to 1 to 80% by weight, storing the solution or emulsion under specific temperature conditions, and then visually checking for changes in the solution or emulsion. For example, in the case of a polyurethane solution (N,N-dimethylformamide/toluene mixture, solids concentration 30% by weight) produced using the polyether polyol of the present invention, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diamine by the above-mentioned two-stage method, the period during which no changes are observed visually in the polyurethane solution when stored at 10°C is preferably 1 month, more preferably 3 months or more, and even more preferably 6 months or more.

<Applications of polyurethane>
The polyurethane using the polyether polyol of the present invention has excellent transparency due to the compatibility of the polyether polyol, good strength, and excellent processability.
It can be widely used in elastomers, elastic fibers, paints, fibers, pressure sensitive adhesives, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, powder paints, active energy radiation curable polymer compositions, etc.

In particular, when polyurethanes using the polyether polyol of the present invention are used for applications such as artificial leather, synthetic leather, water-based polyurethanes, adhesives, elastic fibers, medical materials, and coating agents, the polyurethanes have good low-temperature stability, transparency, and strength, and therefore have good handleability and physical properties in low-temperature environments and are resistant to physical impacts.

[Urethane (meth)acrylate resin]
The polyether polyol of the present invention can be subjected to an addition reaction with a polyisocyanate and a hydroxyalkyl (meth)acrylate to produce a urethane (meth)acrylate oligomer. When other raw material compounds such as a polyol and a chain extender are used in combination, the urethane (meth)acrylate oligomer can be produced by further adding these other raw material compounds to the polyisocyanate. The urethane (meth)acrylate can be blended with other raw materials to produce an active energy ray curable resin composition. This active energy ray curable resin composition can be widely used in various surface processing fields and cast molding applications. When this active energy ray curable resin composition is cured to form a cured film, it has the characteristics of being excellent in balance between hardness and elongation, solvent resistance, and handling, and can be used as a raw material for UV-curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, and photocurable optical fiber coating compositions.

The urethane (meth)acrylate oligomer can be produced by adding a polyisocyanate and a hydroxyalkyl (meth)acrylate, and if necessary, other compounds, in addition to the polyether polyol of the present invention. Examples of polyisocyanates that can be used in producing the urethane (meth)acrylate oligomer include the above-mentioned organic diisocyanates as well as polyisocyanates such as tris(isocyanatohexyl)isocyanurate. Examples of hydroxyalkyl (meth)acrylates that can be used include 2-
As represented by hydroxyethyl (meth)acrylate, there is no particular limitation so long as it is a compound having one or more hydroxyl groups and one or more (meth)acryloyl groups.
Furthermore, in addition to the polyether polyol of the present invention, other polyols and/or compounds having at least two active hydrogens, such as polyamines, may be added as necessary, and these may be used in any combination.

The active energy ray-curable resin composition containing a urethane (meth)acrylate oligomer may be mixed with an active energy ray-reactive monomer other than the urethane (meth)acrylate oligomer, an active energy ray-curable oligomer, a polymerization initiator, a light enhancer, and other additives.

The cured film of the active energy ray curable resin composition containing the urethane (meth)acrylate oligomer can be a film that has excellent stain resistance and protection against common household stains such as ink and ethanol. The laminate using the cured film as a coating for various substrates has excellent design and surface protection properties and can be used as a film to replace paint, and can be effectively applied to, for example, building materials for interior or exterior use, and various components such as automobiles and home appliances.

[(Meth)acrylic resin]
The polyether polyol of the present invention can be derived into a (meth)acrylate by (meth)acrylating one or both of the terminal hydroxyl groups. The (meth)acrylate may be produced by using any of the anhydride, halide, and ester forms of the corresponding (methacrylate). This (meth)acrylate can be blended with other raw materials to give an active energy ray polymerizable composition ((meth)acrylic resin).

This active energy ray-polymerizable composition has the property of being cured by polymerization in a short time by active energy rays such as ultraviolet rays, has excellent transparency due to high compatibility with polyether polyol, and can impart excellent properties to the cured product such as toughness, flexibility, scratch resistance, chemical resistance, etc. From this point of view, it can be used in various fields such as a coating agent for plastics, a molding agent for lenses, a sealant, and an adhesive.

[Polyester elastomer]
The polyether polyol containing an oxymethylene group of the present invention can be used as a polyester-based elastomer.
The polyester elastomer is a copolymer composed of a hard segment mainly made of an aromatic polyester and a soft segment mainly made of an aliphatic polyether, an aliphatic polyester, or an aliphatic polycarbonate.

When the polyether polyol containing an oxymethylene group of the present invention is used as a component of a soft segment, compared with the case where an aliphatic polyether or an aliphatic polyester is used,
The polyether ester elastomer has excellent physical properties such as flexibility, water resistance, and mechanical strength, and has a melt flow rate suitable for blow molding and extrusion molding when melted, and is excellent in balance with mechanical strength and other physical properties, compared with known polyether diols, and can be suitably used for various molding materials including fibers, films, and sheets, such as elastic threads, boots, gears, tubes, and packings. Specifically, the polyether ester elastomer can be effectively used for applications such as joint boots for automobiles and home appliance parts, and wire covering materials.

[Polyester resin]
The polyether polyol containing an oxymethylene group of the present invention can be used as a raw material for polyester resins.
The polyester resin contains a structural unit derived from a thermoplastic polyester resin (a1), a structural unit derived from a polyvalent carboxylic acid, and a structural unit derived from a polyol, and is obtained by polymerizing a polymerization component containing a thermoplastic polyester resin, a polyvalent carboxylic acid, and a polyol. The polyether polyol containing an oxymethylene group of the present invention can be used as the polyol (a3). The polyether polyol containing an oxymethylene group of the present invention has excellent compatibility and tensile strength, and therefore can be used in combination with a polyol (a4).
When used as a3), it exhibits good compatibility with each raw material component of the polyester resin, allowing for a uniform reaction, and it becomes possible to impart good tensile strength to the resulting polyester resin.

In addition, since the polyether polyol containing an oxymethylene group of the present invention has a low glass transition point, it is possible to lower the glass transition point of the polyester-based resin using this as a raw material, and thus to improve the adhesion between the polyester-based resin and the substrate.
The polyester resin can be prepared as a resin composition suitable for adhesive compositions such as adhesives, adhesive sheets, etc., binders for inks such as gravure inks, flexographic inks, offset inks, and screen inks, one-component adhesives, two-component adhesives, hot melt adhesives, and moisture-curable hot melt adhesives. That is, the polyester resin composition preferably contains a hydrolysis inhibitor (
The polyester resin composition contains a crosslinking agent (B), a crosslinking agent (C), and may contain a pigment (D), a urethane catalyst (E), an antioxidant (F), etc. The pigment (D) is preferably contained particularly when the polyester resin composition is used for ink applications.

[Polyester resin for coating]
The polyether polyol containing an oxymethylene group of the present invention can be used as a raw material for polyester resins for coating.
The polyester resin for coating is a polymer obtained by polycondensation of a carboxylic acid or its alkyl ester compound (for example, methyl ester) with a polyalcohol compound.

The polyester resin for coating obtained by the above method is used in a state where the polyester resin for coating and a crosslinking agent are dissolved in an organic solvent. Examples of the organic solvent to be used include aromatic hydrocarbons such as toluene, xylene, and Solvesso, esters such as ethyl acetate, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone, and ethers such as ethyl cellosolve and butyl cellosolve.

The polyether polyol containing oxymethylene groups of the present invention has excellent compatibility, so when it is used as a raw material for polyester resins for coating, it can improve the solubility of the resulting polyester resin in various organic solvents. In addition, since the solubility in various organic solvents is improved, it becomes possible to select solvents with low environmental impact that could not be used before due to insufficient solubility.
The polyester resin for coating thus obtained can be used for beverage cans, food cans, their lids, caps, etc. It can be used by coating the inner and outer surfaces of any metal plate, such as tinplate, tin-free steel, aluminum, etc. These metal plates may be surface-treated in advance with phosphate treatment, chromate treatment, phosphate chromate treatment, or other rust-preventive agents for the purpose of preventing corrosion and improving the adhesion of the coating film.

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

<Molecular Weight and Molecular Weight Distribution of Polyether Polyol>
The number average molecular weight (Mn
), measure the weight average molecular weight (Mw), and calculate the weight average molecular weight Mw (GPC) / number average molecular weight M
The molecular weight distribution was calculated by n (GPC) and the molecular weight distribution (D).

Measurement method by GPC: The weight average molecular weight Mw and number average molecular weight Mn in terms of polystyrene were determined by GPC measurement under the following conditions.
Equipment: Tosoh HLC-8220
Column: TSKgel Super HZM-N
(4.6mm I.D. x 15cm L x 4)
Reference column: TSKgel Super H-RC
(6.0mm I.D. x 15cm L x 1 piece)
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Column temperature: 40°C
RI detector: RI (built into the device HLC-8220)

<Oxymethylene Linkage Bond Ratio>
50 mg of the prepared polyether polyol was dissolved in 0.75 mL of CDCl ₃ and
00MHz ^1H -NMR (ECZ-400S manufactured by JEOL Ltd.) was measured.
The sum of the integral values of the singlet peaks observed between 4.8 ppm and 4.8 ppm (hereinafter referred to as "A"
), and the integral value (hereinafter "B") of the peak observed at the highest magnetic field among the singlet peaks observed between 4.5 ppm and 4.8 ppm was measured, and (A-B)/A was calculated. (A-B)/A was defined as the oxymethylene linkage bond ratio in the polyether polyol.

<Molecular weight of polyurethane>
The polyurethane was dissolved in dimethylacetamide (containing about 0.3% by weight of lithium bromide (anhydrous)) to a concentration of 0.07% by weight, and used as a sample for GPC measurement.
Sample injection volume: about 40 μL, column temperature: 40° C., measurement solvent (mobile phase):
Dimethylacetamide (containing about 0.3% by weight of lithium bromide (anhydrous)), flow rate: 0.6 mL/
The molecular weight of the polyurethane was measured under the measurement conditions of 1000 sq. m. min. The molecular weight of the polyurethane was expressed as a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of standard polystyrene using a commercially available monodisperse polystyrene solution as a standard sample.

<Tensile test evaluation of polyurethane>
The polyurethane solution was applied onto a fluororesin sheet (fluoro tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 500 μm applicator, and then left at 80° C. for 1 hour.
The polyurethane film was then dried at 100° C. for 0.5 hours. After further drying at 100° C. in a vacuum for 0.5 hours, the polyurethane film was allowed to stand at a constant temperature and humidity of 23° C. and 60% RH for 12 hours or more. A test piece of 1 cm×15 cm was cut out from the polyurethane film obtained.
301 (2010), a tensile tester (Shimadzu Corporation, product name "AGS-X") was used.
) at a chuck distance of 50 mm, a pulling speed of 500 mm/min, and a temperature of 23°C or -
A tensile test was carried out under a temperature condition of 10°C and a relative humidity of 60%, and the stress at the time when the test piece was elongated by 100% (100% modulus) and the stress at the time when the test piece was elongated by 300% (300% modulus) were measured. A test piece with a 100% modulus of 5 MPa or less is excellent in flexibility, and a test piece with a 300% modulus of 7 MPa or more is excellent in elasticity. The elongation and strength at the time when the test piece broke were also measured. The greater the elongation and the higher the strength, the better the flexibility and mechanical strength.

[Compound abbreviation]
The abbreviations for the compounds used in the examples and comparative examples are as follows.
PTMG: Polyoxytetramethylene glycol (number average molecular weight 652) manufactured by Mitsubishi Chemical Corporation PFA: Paraformaldehyde manufactured by Tokyo Chemical Industry Co., Ltd. BG: 1,4-butanediol manufactured by Mitsubishi Chemical Corporation MDI: 4,4'-diphenylmethane diisocyanate (product name "MILLIONATE") manufactured by Mitsubishi Chemical Corporation
U-830: Neostan U-830 manufactured by Tosoh Corporation DMF: Dehydrated N,N-dimethylformamide manufactured by Nitto Kasei Co., Ltd. DIAION RCP160M: Sulfonic acid-based strong acid cation exchange resin manufactured by Wako Pure Chemical Industries, Ltd. Montmorillonite K10: Aldrich Co., Ltd.

[Example 1]
(Polyether polyol)
In a 300 mL glass 4-neck flask equipped with a mechanical stirrer and a Dean-Stark trap, 130 g of PTMG, 5.0 g of PFA, and 4 g of DIAION RCP160M were added.
.4g, toluene 40mL, and replaced with nitrogen gas. The flask was heated in a 120 ° C oil bath, and reacted at normal pressure for 4 hours while removing water under reflux conditions. The catalyst was removed from the reaction solution by suction filtration with filter paper. The pressure was then set to 1 mmHg, and the solution was heated at a maximum temperature of 140 ° C for 5 hours to remove the solvent, obtaining a polyether polyol. The results are shown in Table 1.

(Polyurethane)
Using the obtained polyether polyol as a raw material, polyurethane was produced by the solvent-based one-shot method according to the following procedure. A separable flask equipped with a thermocouple, a cooling tube, and a stirrer was placed on a 60°C oil bath, and 69.85 g of polyether polyol heated to 80°C, 5.72 g of BG, and 231.77 g of DMF were placed in the separable flask, and 0.0183 g of U-830 was added as a urethane catalyst. Then, 21.57 g of MDI was added.
The contents of the separable flask were heated to 70° C. in about 1 hour under a nitrogen atmosphere while stirring at 60 rpm. After the temperature reached 70° C., the mixture was stirred for another 0.5 hours.
The molecular weight of the polyurethane was adjusted by adding in portions to obtain a polyurethane. The evaluation results of the polyurethane are shown in Table 1.

[Comparative Example 1]
(Polyether polyol)
Polyether polyol was synthesized by the method described in Patent Document 3. 3 L of PTMG was placed in a 1 L glass separable flask equipped with a mechanical stirrer and a Dean-Stark trap.
08g, 13.0g PFA, 0.31g paratoluenesulfonic acid monohydrate, and 107mL toluene were added, and replaced with nitrogen gas. The 1L glass separable flask was heated in an oil bath with an upper limit of 120°C, and reacted at normal pressure for 2 hours while stirring and removing water under reflux conditions. Then, a separation process was carried out using ethyl acetate and pure water to remove the catalyst. The organic phase was separated, heated under reduced pressure, and water and solvent were removed to obtain a polyether polyol. The results are shown in Table 1.

(Polyurethane)
The resulting polyether polyol was used as a raw material to obtain a polyurethane in the same manner as in Example 1. The evaluation results of the polyurethane are shown in Table 1.

[Comparative Example 2]
(Polyether polyol)
Polyether polyol was synthesized by the method described in Patent Document 1. 250 g of PTMG, 11.6 g of PFA, 13.9 g of Montmorillonite K10, and 193 mL of cyclohexane were placed in a 1 L glass four-neck flask equipped with a magnetic stirrer and a Dean-Stark trap.
The atmosphere was replaced with nitrogen gas. The 1 L glass four-neck flask was heated in an oil bath with a maximum temperature of 90° C., and the reaction was carried out at normal pressure for 4 hours while stirring and removing water under reflux conditions.
The montmorillonite K10 was removed by filtration through a celite bed supported on a glass filter to obtain a reaction liquid.

Next, 90 mL of deionized water and the reaction solution were placed in a four-neck flask equipped with an oil bath, a magnetic stirrer, a steam source with a condensation trap, a nitrogen purge, and a Liebig condenser. While adding 12.8 g of calcium hydroxide, steam was introduced under stirring, and 950 mL of water was collected by steam distillation. The contents of the flask were then cooled to 80°C, 50 mL of toluene was added, and the solids were removed by vacuum filtration using filter paper and transferred to a separatory funnel. The upper phase was separated to obtain an organic phase containing polyether polyol. The organic phase was purged with nitrogen gas at 120°C, and toluene and water were distilled off under reduced pressure using a rotary evaporator to obtain a crude polyether polyol containing a trace amount of water. 130 mL of toluene and 10.3 g of calcium oxide were added to the crude polyether polyol, and the mixture was stirred overnight to obtain a slurry. The slurry was filtered through a celite bed, and volatile components were distilled off under reduced pressure at 120°C to obtain a polyether polyol. The results are shown in Table 1.

(Polyurethane)
The resulting polyether polyol was used as a raw material to obtain a polyurethane in the same manner as in Example 1. The evaluation results of the polyurethane are shown in Table 1.

As is clear from the above table, the polyether polyol of the present invention is a polyether polyol that can efficiently produce polyurethane when used as a raw material to produce polyurethane, and the polyurethane produced has improved tensile strength and elongation at break. On the other hand, when polyurethane is produced using the polyether polyol of the comparative example as a raw material, the polyurethane has reduced tensile strength or poor elongation at break. Furthermore, the number average molecular weight of the polyether polyol of Comparative Example 1 is 99.7% of the number average molecular weight of the polyether polyol of Example 1, which is almost the same level, but the number average molecular weight of the polyurethane of Comparative Example 1 produced using each polyether polyol is reduced to 54% of the number average molecular weight of the polyurethane of Example 1.
From the above, the polyether polyol of the present invention has excellent compatibility with urethane raw materials, has good reactivity as a urethane raw material, and has a significantly higher number average molecular weight than the polyurethane using the polyether polyol of Comparative Example 1. In addition, it is clear that this is a polyether polyol that can exhibit excellent tensile resistance when made into a polyurethane, and is therefore suitable for use in elastic fibers,
It is expected to be used as a raw material for polyurethane and polyester, which are used for various applications such as artificial leather.

Claims (2)

A polyether polyol represented by the following formula (1):
The ratio of the amount of oxymethylene groups bonded to each other to the total amount of oxymethylene groups is 8.
0% or less and a molecular weight distribution of 1.85 or more.

In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n represents an integer of 1 to 40.
where m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple R may be the same or different. 2. The polyether polyol according to claim 1, wherein the number average molecular weight of the polyether polyol is 600 or more and 9,900 or less.
The polyether polyol described in .