JP2023149599A - Polyalkylene ether glycol and method for producing the same - Google Patents

Abstract

To provide a polyalkylene ether glycol that has excellent heat resistance, and to provide a method for producing a polyalkylene ether glycol that has excellent low coloring property.SOLUTION: Provided is a polyalkylene ether glycol represented by the following formula (1). HO-(R1-O)n-(R2-O)m-H (1). In the formula (1), R1 represents a divalent hydrocarbon group derived from a dimer diol having 36 to 44 carbon atoms, which is a reduced cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids, R2 represents an alkylene group having 2 to 18 carbon atoms, n and m each independently represent a real number of 0 or more, and n/(n+m) is 0.1 or more.SELECTED DRAWING: None

Description

The present invention relates to a polyalkylene ether glycol and a method for producing the same.

Polyether polyols are polyols that have a wide range of uses, including as raw materials for soft segments such as elastic fibers, thermoplastic elastomers, and thermosetting elastomers. As typical polyether polyols, polyalkylene ether glycols such as polyethylene glycol and polytetramethylene ether glycol are known.

However, polyalkylene ether glycol, which is composed of alkylene diols with short carbon chains such as polytetramethylene ether glycol, may have poor physical properties such as thermal stability, and when blended with urethane or polyester to make a resin, This results in negative results such as a decrease in pyrolysis temperature and generation of decomposition gas. For this reason, polyalkylene ether glycols having higher thermal stability are desired depending on the application. Therefore, in recent years, polyalkylene ether glycols produced using alkylene diols with long carbon chains as monomers have been attracting attention; for example, polydecamethylene ether glycols using 1,10-decane diol are known ( For example, non-patent document 1).

As a method for producing polydecamethylene ether glycol, for example, 1,10-decanediol is polycondensed using a polycondensation catalyst such as sulfuric acid or a cation exchange resin having a sulfone group, and polydecamethylene ether glycol having a number average molecular weight of 900 to 4000 is produced. There is a method for obtaining methylene ether glycol (for example, Non-Patent Document 2).

It is also known that sulfuric acid esters contained in polyalkylene ether glycol produced by polycondensation using sulfuric acid as a catalyst cause emulsification during washing with water, making it difficult to remove the catalyst by washing with water. Therefore, it has been proposed to treat polyalkylene ether glycol consisting of alkanediol having 2 to 20 carbon atoms produced by polycondensation with sulfuric acid in an acidic aqueous solution. Those with a value of 0.03 to 0.1 have been obtained (for example, Patent Document 1).

International Publication No. 99/01496

Journal of Applied Polymer Science 65 7 1997 p. 1319-1332 Polymer International 27 1992 p. 275-283

However, according to studies conducted by the present inventors, even when polyalkylene ether glycol having a long-chain alkylene group such as polydecamethylene ether glycol is used, heat generation due to the volatilization of low molecular weight components under heating conditions occurs. It has been observed that the decomposition temperature is lower and the heat resistance is poorer. In addition, in the above-mentioned production method, since an acid catalyst is used, there is a problem that the polyalkylene ether glycol tends to be colored.

The present invention was made in view of the above-mentioned circumstances, and its purpose is to provide a polyalkylene ether glycol with excellent heat resistance, and to provide a method for producing polyalkylene ether glycol with excellent low coloring property. .

As a result of intensive studies in view of the problems of the prior art, the present inventors have identified the use of polyalkylene ether glycol represented by the following formula (1) and the use of polyalkylene ether glycol as an acid catalyst in the method for producing polyalkylene ether glycol. The inventors have discovered that the above object can be achieved by using a concentrated acid catalyst aqueous solution, and have completed the present invention. That is, the gist of the present invention is as follows.

[1] Polyalkylene ether glycol represented by the following formula (1).
HO-(R ¹ -O) _n -(R ² -O) _m -H...(1)
(In formula (1), R ¹ is a divalent diol derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a hydrocarbon group, ^R2 represents an alkylene group having 2 to 18 carbon atoms, n and m each independently represent a real number of 0 or more, and n/(n+m) is 0.1 or more.)
[2] The polyalkylene ether glycol according to [1], wherein n/(n+m) in the formula (1) is 0.25 or more.
[3] The polyalkylene ether glycol according to [1] or [2], which has a number average molecular weight calculated from a hydroxyl value of 300 to 5,000.
[4] The polyalkylene ether glycol according to any one of [1] to [3], which has a molecular weight distribution of 1.1 to 3.0.
[5] The polyalkylene ether glycol according to any one of [1] to [4], wherein in the formula (1), R ² is a 1,10-decylene group.
[6] A method for producing polyalkylene ether glycol, comprising a step of dehydrating and condensing a glycol component using an acid catalyst,
A method for producing polyalkylene ether glycol, wherein in the dehydration condensation step, an aqueous acid catalyst solution having a concentration of 70% by weight or less is used as the acid catalyst.
[7] The method for producing polyalkylene ether glycol according to [6], wherein the polyalkylene ether glycol is represented by the following formula (1).
HO-(R ¹ -O) _n -(R ² -O) _m -H...(1)
(In formula (1), R ¹ is a divalent diol derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a hydrocarbon group, ^R2 represents an alkylene group having 2 to 18 carbon atoms, and n and m each independently represent a real number of 0 or more.)

According to the present invention, it is possible to provide a polyalkylene ether glycol that is excellent in heat resistance, and to provide a method for producing a polyalkylene ether glycol that is excellent in low coloring property.

Embodiments of the present invention will be described in detail below. The explanation of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof.

[Polyalkylene ether glycol]
The polyalkylene ether glycol (hereinafter also referred to as "compound (A)") of the present invention has a structure represented by the following formula (1).
HO-(R ¹ -O) _n -(R ² -O) _m -H...(1)
In formula (1), R ¹ is a divalent carbonized diol derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a hydrogen group, R ² represents an alkylene group having 2 to 18 carbon atoms, n and m each independently represent a real number of 0 or more, (n+m)>1 is satisfied, and n/(n+m) is 0. It is 1 or more.

In formula (1), n and m each independently represent a real number of 0 or more.
n is preferably 0.1 to 50, more preferably 0.2 to 25, and even more preferably 0.3 to 10.
When n is equal to or greater than the above lower limit, high thermal stability is likely to be imparted.
When n is less than or equal to the above upper limit, crystallinity becomes low and flexibility can be imparted.
m is preferably from 0 to 100, more preferably from 0 to 50, even more preferably from 0 to 25.
When m is equal to or greater than the above lower limit, high thermal stability is likely to be imparted.
When m is below the above upper limit, crystallinity becomes low and flexibility can be imparted.

n/(n+m) is 0.1 or more.
n/(n+m) is more preferably from 0.1 to 1, even more preferably from 0.25 to 1.
When n/(n+m) is greater than or equal to the above lower limit, high thermal stability is likely to be imparted.

In formula (1), R ¹ is a divalent hydrocarbon derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a group.
Examples of the dimer diol include a compound represented by the following formula (2).
HO-(CH ₂ ) _s -Y-(CH ₂ ) _t -OH...(2)
In formula (2), Y represents a linear, branched, or cyclic divalent hydrocarbon group having 16 to 42 carbon atoms which may have a substituent, and s represents an integer of 1 to 10. where t represents an integer from 1 to 10.
Y is a straight chain, branched chain, or cyclic divalent hydrocarbon group having 16 to 42 carbon atoms which may have a substituent. The number of carbon atoms in Y may be 16 to 36 or 18 to 30.
The divalent hydrocarbon group may be a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group.
Examples of the substituent include a straight chain, branched chain, or cyclic alkyl group having 1 to 10 carbon atoms, or a straight chain, branched chain, or cyclic alkenyl group having 2 to 10 carbon atoms.
s is an integer of 1 to 10, preferably an integer of 6 to 10, and preferably an integer of 6 to 8.
t is an integer of 1 to 10, preferably an integer of 6 to 10, and preferably an integer of 6 to 8.

When the dimer diol is a linear dimer diol obtained by reducing an acyclic dimer acid, in formula (2), Y is a group represented by the following formula (3). It is preferable that there be.
-R ^a1 -X-R ^a2 - ...(3)
In formula (3), R ^a1 and R ^a2 each independently represent a straight chain alkylene group having 8 to 21 carbon atoms or a straight chain alkenylene group having 8 to 21 carbon atoms, and X is a single bond, Or represents -O-.
Alkenylene groups contain 1 to 3 unsaturated bonds.

When the dimer diol is a dimer diol having a branched structure obtained by reducing an acyclic dimer acid, in formula (2), Y is a group represented by the following formula (4). It is preferable that there be.
-CH(R ^b1 )-CH(R ^b2 )- (4)
In formula (4), R ^b1 and R ^b2 each independently represent a straight chain alkylene group having 8 to 20 carbon atoms or a straight chain alkenylene group having 8 to 20 carbon atoms.
Alkenylene groups contain 1 to 3 unsaturated bonds.

When the dimer diol is a dimer diol having a cyclic structure obtained by reducing a cyclic dimer acid, in formula (2), Y is a group represented by the following formula (5). It is preferable.

In formula (5), ring C represents a saturated hydrocarbon ring having 5 to 14 carbon atoms or an unsaturated hydrocarbon ring having 5 to 14 carbon atoms, p is an integer of 1 to 6, and R ^c1 is each It independently represents a straight chain alkylene group having 1 to 16 carbon atoms or a straight chain alkenylene group having 1 to 16 carbon atoms.
Ring C may be a monocyclic ring or may be a condensed ring in which two or more monocycles are condensed. The monocyclic ring may be a 5-membered ring or a 6-membered ring.
p is an integer from 1 to 6, and is an integer equal to or less than the number of carbon atoms in ring C minus 2. When Ring C is a 6-membered monocyclic ring, p is 1 to 4; when Ring C is a condensed ring in which two 6-membered monocycles are fused, p is 1 to 6.
An unsaturated hydrocarbon ring contains 1 to 3 unsaturated bonds.
Alkenylene groups contain 1 to 3 unsaturated bonds.

The dimeric diol constituting the alkylene group of ^R1 can be obtained by dimerizing an unsaturated fatty acid having 18 to 22 carbon atoms and reducing the resulting cyclic or acyclic dimer acid. .
Here, "cyclic dimer acid" means a dimer acid that has a cyclic structure, and "acyclic dimer acid" means a dimer acid that does not have a cyclic structure. do.
Examples of unsaturated fatty acids having 18 to 22 carbon atoms include oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, β-eleostearic acid, and stearidone. Examples include gadoleic acid, eicosenoic acid, eicosadienoic acid, Mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, arachidonic acid, eicosatetraenoic acid, erucic acid, docosadienoic acid, and adrenic acid. Among these, oleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, and erucic acid are preferred from the viewpoint of easy availability.

Examples of the dimer diol having a branched structure obtained by reducing an acyclic dimer acid include compounds represented by the following structural formula.

Examples of the dimer diol having a cyclic structure obtained by reducing a cyclic dimer acid include compounds represented by the following structural formula.

In formula (1), R ¹ is preferably a divalent hydrocarbon group represented by formula (7) below.
-(CH ₂ ) _s -Y-(CH ₂ ) _t - (7)
In formula (7), Y, s, and t are the same as those described above.

In formula (1), R ² represents an alkylene group having 2 to 18 carbon atoms. R ² is preferably an alkylene group having 6 to 16 carbon atoms, more preferably an alkylene group having 8 to 14 carbon atoms, and even more preferably an alkylene group having 8 to 12 carbon atoms.
As R ² , 1,6-hexylene group (-(CH ₂ ) ₆ -), 1,7-heptylene group (-(CH ₂ ) ₇ -), 1,8-octylene group (-(CH ₂ ) ₈ -), 1,9-nonylene group (-(CH ₂ ) ₉ -), 1,10-decylene group (-(CH ₂ ) ₁₀ -), undecylene group (-(CH ₂ ) ₁₁ -), dodecylene group (-(CH ₂ ) ₁₂ -), octadecylene (-(CH ₂ ) ₁₈ -), etc., among which 1,10-decylene group is preferred.

The degree of polymerization (that is, n+m) of compound (A) is preferably 1 to 15, more preferably 1.1 to 13, even more preferably 1.2 to 12, and 1.3. -11 are particularly preferred.
When the degree of polymerization of the compound (A) is at least the above lower limit, the effect of increasing the molecular entanglement required for the soft segment of the elastomer is likely to be obtained.
When the degree of polymerization of the compound (A) is below the above upper limit, crystallinity becomes low and flexibility can be imparted.
In this specification, the degree of polymerization is a value calculated from the integrated intensity ratio of methylene chains bonded to terminal hydroxyl groups and methylene chains bonded to ether groups using nuclear magnetic resonance spectroscopy.

The number average molecular weight (hereinafter also referred to as "number average molecular weight (1)") of compound (A) in terms of standard polystyrene molecular weight is preferably 300 to 5,000, and preferably 500 to 3,000. More preferably, it is from 700 to 2,500, and particularly preferably from 800 to 2,300.
When the number average molecular weight (1) of the compound (A) is at least the above lower limit, the effect of increasing the molecular entanglement required for the soft segment of the elastomer is likely to be obtained.
When the number average molecular weight (1) of the compound (A) is less than or equal to the above upper limit, the crystallinity becomes low and the effect of imparting flexibility is likely to be obtained.
In this specification, the number average molecular weight (1) is a value calculated from a polystyrene calibration curve using GPC.

The mass average molecular weight of compound (A) is preferably 300 to 25,000, more preferably 500 to 12,000, even more preferably 700 to 6,900, and even more preferably 800 to 4,600. is particularly preferred.
When the mass average molecular weight of the compound (A) is at least the above lower limit, the effect of increasing the molecular entanglement required for the soft segment of the elastomer can be easily obtained.
When the mass average molecular weight of the compound (A) is less than or equal to the above upper limit, the crystallinity becomes low and the effect of imparting flexibility is likely to be obtained.
In this specification, the mass average molecular weight is a value calculated from a polystyrene calibration curve using GPC.

The molecular weight distribution of compound (A) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, even more preferably 1.1 to 3.0, Particularly preferred is 1.1 to 2.0.
When the molecular weight distribution of the compound (A) is less than or equal to the above upper limit, the effect that the quality is easily stabilized is easily obtained when polymerizing the polyalkylene ether glycol as a monomer.
In this specification, molecular weight distribution is expressed as [mass average molecular weight]/[number average molecular weight (1)], and is a value calculated from the mass average molecule obtained using GPC and the number average molecular weight (1). be.

The terminal olefination rate of compound (A) is preferably 10.0 mol% or less, more preferably 5.0 mol% or less, even more preferably 2.0 mol% or less, and 1.0 mol% or less. is particularly preferred.
When the terminal olefinization rate of the compound (A) is below the above upper limit, the effect of improving the degree of polymerization of the polymer is likely to be obtained when the polyalkylene ether glycol is polymerized as a monomer. In this specification, the terminal olefination rate can be calculated by the method described in Examples using ¹ H-NMR.

The terminal esterification rate of compound (A) is preferably 2.0 mol% or less, more preferably 1.5 mol% or less, even more preferably 1.0 mol% or less, and even more preferably 0.8 mol% or less. is particularly preferred.
When the terminal esterification rate of the compound (A) is below the above upper limit value, the effect of improving the degree of polymerization of the polymer is likely to be obtained when the polyalkylene ether glycol is polymerized as a monomer.
In this specification, the terminal esterification rate can be calculated by the method described in Examples using ¹ H-NMR.

The hydroxyl value of compound (A) is preferably 20 to 400, more preferably 35 to 220, even more preferably 40 to 160, particularly preferably 50 to 150.
When the hydroxyl value of the compound (A) is greater than or equal to the lower limit, crystallinity becomes low and flexibility can be imparted.
When the hydroxyl value of the compound (A) is below the above upper limit, the effect of increasing the molecular entanglement required for the soft segment of the elastomer is likely to be obtained.
In this specification, the hydroxyl value can be measured by the method described in Examples.

The number average molecular weight (hereinafter also referred to as "number average molecular weight (2)") calculated from the hydroxyl value of compound (A) is preferably 300 to 5,000, and preferably 500 to 3,000. is more preferable, more preferably 700 to 2,500, particularly preferably 750 to 2,000.
When the number average molecular weight (2) of the compound (A) is at least the above lower limit, the effect of increasing the molecular entanglement required for the soft segment of the elastomer is likely to be obtained.
When the number average molecular weight (2) of the compound (A) is less than or equal to the above upper limit, the crystallinity becomes low and the effect of imparting flexibility is likely to be obtained.
In this specification, the number average molecular weight (2) can be calculated from the hydroxyl value by the method described in Examples.

The 5% weight loss temperature of compound (A) is preferably 250 to 500°C, more preferably 270 to 450°C, even more preferably 280 to 400°C, and even more preferably 300 to 380°C. It is particularly preferable.
When the 5% weight loss temperature of the compound (A) is equal to or higher than the above lower limit, the effect of increasing heat resistance is likely to be obtained.
In this specification, the 5% weight loss temperature can be measured by the method described in Examples.

(Production method of polyalkylene ether glycol)
The method for producing polyalkylene ether glycol of the present invention is not particularly limited, but it can be produced by dehydrating and condensing glycol components using an acid catalyst.

<Glycol component>
The glycol component is a dimeric diol containing 36 to 44 carbon atoms that is normally present in alcohols obtained by reducing cyclic and acyclic dimer acids obtained by dimerizing unsaturated fatty acids. include.
Examples of the dimer diol include a compound represented by the following formula (2).
HO-(CH ₂ ) _s -Y-(CH ₂ ) _t -OH...(2)
In formula (2), Y, s, and t are the same as those described above.

The glycol component may further contain a diol having an alkylene group having 2 to 18 carbon atoms.
Examples of diols having an alkylene group having 2 to 18 carbon atoms include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol , 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol and the like. Among the above, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and 1,18-octadecanediol are preferred from the viewpoint of thermal stability and melting point when made into a polymer, and 1,10-decanediol is most preferred from the viewpoint of availability and availability.

In the glycol component, the proportion of dimer diol is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and 25 to 100 mol% based on the total number of moles of the glycol component. is even more preferable.
When the glycol component contains a diol having an alkylene group having 2 to 18 carbon atoms, the proportion of the dimer diol is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, and 25 to 90 mol%. % is more preferable.
When the proportion of the dimer diol is at least the above lower limit, the effect of increasing heat resistance is likely to be obtained.
When the proportion of the dimer diol is below the above upper limit, the effect of improving the melting point is likely to be obtained.

When the glycol component contains a diol having an alkylene group having 2 to 18 carbon atoms, the proportion of the diol having an alkylene group having 2 to 18 carbon atoms should be 1 to 90 mol% with respect to the total number of moles of the glycol component. is preferable, more preferably 5 to 80 mol%, even more preferably 10 to 75 mol%.
When the proportion of the diol having an alkylene group having 2 to 18 carbon atoms is at least the above lower limit, the effect of improving the melting point is likely to be obtained.
When the proportion of the diol having an alkylene group having 2 to 18 carbon atoms is below the above upper limit, the effect of increasing heat resistance is likely to be obtained.

The dehydration condensation reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary as long as the reaction system is maintained in a liquid phase, and normal pressure conditions are usually employed. If desired, the reaction may be carried out under reduced pressure or an inert gas may be passed through the reaction system in order to promote desorption of water produced by the reaction from the reaction system.

The reaction temperature is usually 80 to 250°C, preferably 100 to 200°C, more preferably 120 to 180°C. If the reaction temperature is too high, the raw materials tend to volatilize, the amount of terminal unsaturated groups increases, or the polymer tends to become colored; if the reaction temperature is too low, a sufficient reaction rate cannot be obtained. Tend.

The reaction time varies depending on the amount of catalyst used, reaction temperature, yield and physical properties of the produced polymer, etc., but is usually 0.5 to 50 hours, preferably 1 to 20 hours. Incidentally, the reaction is usually carried out without a solvent, but a solvent can also be used if desired. The solvent may be appropriately selected from organic solvents commonly used in organic synthesis reactions. Examples include ethers such as tetrahydrofuran, diethyl ether, and dibutyl ether, hydrocarbons such as decane, toluene, and xylene, and amides such as N,N-dimethylformamide and N,N-dimethylacetamide.

The dehydration condensation catalyst (also referred to as polycondensation catalyst) only needs to be capable of producing polyalkylene ether glycol through the dehydration condensation reaction of alkylene diol, and acid catalysts are usually used. Examples of acid catalysts include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; heteropolyacids such as phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, and silicotungstic acid; zeolite, montmorillonite, and cation exchange resins. , sulfuric acid trace metal oxides, solid catalysts such as metal organic frameworks (MOF); carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, benzenesulfonic acid, Examples include sulfonic acids such as p-toluenesulfonic acid, naphthalenesulfonic acid, and 10-camphorsulfonic acid; Lewis acids such as scandium trifluoromethanesulfonate and zinc trifluoromethanesulfonate. Preferred are acids with sulfonic groups from the viewpoint of acid strength and corrosivity, such as sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and 10-camphor. Sulfonic acid is preferred, and sulfuric acid and p-toluenesulfonic acid are more preferred from the viewpoint of cost.

When using an acid having a sulfonic group (-SO ₃ H) in the dehydration condensation reaction, the amount used varies depending on the type of catalyst, but is usually 1 to 20 parts by weight, preferably 1 to 100 parts by weight of the glycol component. The amount is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

As the acid catalyst, it is preferable to use an aqueous acid catalyst solution. The concentration of acid in the acid catalyst aqueous solution is preferably 90% by weight or less, more preferably 1 to 80% by weight, and preferably 5 to 70% by weight, based on the total weight of the acid catalyst aqueous solution. More preferred.
When the concentration of acid in the acid catalyst aqueous solution is equal to or higher than the above lower limit, the dehydration condensation reaction tends to proceed.
When the concentration of acid in the acid catalyst aqueous solution is below the above upper limit, coloring upon addition of acid can be easily reduced.
<Hydrolysis>

Polyalkylene ether glycol obtained by performing a dehydration condensation reaction in the presence of a polycondensation catalyst such as an acid catalyst usually has a portion of the terminal end as an ester group, so it is hydrolyzed in an acidic or basic aqueous solution. By doing so, the terminal ester group can be returned to a hydroxyl group.
The hydrolysis temperature is higher than 60°C and lower than 200°C, preferably higher than 80°C and lower than 180°C, more preferably higher than 100°C and lower than 160°C. If the temperature is too high, there is a risk of decomposition of parts other than the terminal ends of the polymer, and if the temperature is too low, there is a tendency that a sufficient reaction rate cannot be obtained.
When the reaction temperature is within the above range, it is preferably carried out under reflux or in a closed reactor such as an autoclave.
The reaction time varies depending on the concentration of the acid or base, the reaction temperature, the amount of terminal ester groups of the polyalkylene ether glycol, etc., but is usually 1 to 50 hours, preferably 2 to 30 hours, and more preferably 3 to 20 hours.
Polyalkylene ether glycols obtained by performing a dehydration condensation reaction in the presence of a superacid such as trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid as a polycondensation catalyst usually do not produce an ester group at the end, so they are difficult to process in the hydrolysis process. can be omitted.

Water is usually used as the reaction solvent, but an organic solvent can also be used in combination if desired. The organic solvent may be appropriately selected from organic solvents used in ordinary organic synthesis reactions, and in addition to the above-mentioned organic solvents, alcohols such as isopropanol and butanol can also be used. The amount of water added during hydrolysis varies depending on the concentration of acid or base, but is usually 0.1 to 200 parts by weight, preferably 0.5 to 150 parts by weight, more preferably 0.5 to 150 parts by weight, per 100 parts by weight of polyalkylene ether glycol. is 2 to 100 parts by weight. If the amount of water used in the reaction is too small, the amount of terminal unsaturated groups may increase, and if the amount of water is too large, a larger reactor will be required, which is not preferable.

As described above, the hydrolysis reaction is carried out in an acidic or basic aqueous solution, but the acid catalyst used in the dehydration condensation may be used as is, or an acid or base may be newly added. Examples of acids used include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, Sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, naphthalenesulfonic acid, and 10-camphorsulfonic acid can be used. Bases include alkali metal or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, etc. Carbonates; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. can be used, but alkali metal hydroxides are preferred, and sodium hydroxide and potassium hydroxide are more preferred from the viewpoint of water solubility. preferable.
The amount of acid or base in the hydrolysis reaction varies depending on the amount and type of acid in the dehydration condensation reaction, but is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of water added. be.

<Oil/water separation process>
The production method of the present invention preferably includes an oil-water separation step after the hydrolysis reaction in order to reduce acids, bases, salts, etc. contained in the reaction solution. The oil/water separation step is a step of separating a polyalkylene ether glycol layer and an aqueous layer containing acids, bases, salts, and the like. In addition, when the value of the number of hydroxyl groups of the polyalkylene ether glycol obtained after the dehydration condensation reaction is 1.970 to 1.999, oil-water separation is performed after the dehydration condensation reaction without going through the hydrolysis reaction. Good too.

The temperature in the oil/water separation step is preferably higher than the melting point of the polyalkylene ether glycol. Although it varies depending on the number of carbon atoms in the alkylene chain of the polyalkylene ether glycol and the molecular weight of the polyalkylene ether glycol to be produced, for example, if it is a polydecamethylene ether glycol with a melting point of 75 to 80°C and a number average molecular weight of 1000, an oil-water separation process is required. The temperature is preferably 80°C or higher. Usually, an organic solvent is not used, but if the polyalkylene ether glycol has a high viscosity and the operability of layer separation is not good, an organic solvent may be used. When an organic solvent is used, the temperature is usually 20°C or higher, more preferably 40°C or higher, although it varies depending on the type of organic solvent and the concentration and molecular weight of the polyalkylene ether glycol. If the temperature is too low, polyalkylene ether glycol tends to precipitate, making oil/water separation difficult.
The separation time in the oil-water separation step is not particularly limited, but is usually 0.01 to 10 hours, preferably 0.2 to 7 hours, and more preferably 0.5 to 5 hours. If the separation time is too short, the separation properties between the oil layer and the water layer tend to be poor, and if the separation time is too long, the productivity tends to deteriorate.
If acids, bases, salts, etc. remain in the polymer layer obtained by layer separation, water is added again and oil-water separation is repeated to remove remaining impurities.

[Application]
The polyalkylene ether glycol of the present invention can be used as a raw material for polyester, polycarbonate, polyurethane resin, etc.
As a method for producing polyester using the polyalkylene ether glycol of the present invention as a raw material, conventional methods for producing polyester can be employed. For example, to give an example of a method for producing a polyether ester copolymer, in the presence of a catalyst, a diester compound of an aromatic dicarboxylic acid, an excess amount of aliphatic and/or alicyclic diol, and the polyalkylene ether glycol of the present invention. A method of transesterifying and subsequently polycondensing the obtained reaction product under reduced pressure, in the presence of a catalyst, an aromatic dicarboxylic acid, an aliphatic and/or alicyclic diol, and the polyalkylene ether glycol of the present invention. A method in which a short-chain polyester (e.g., polybutylene terephthalate) is prepared in advance, and this is combined with other aromatic dicarboxylic acids and the polycondensate of the present invention. A method of polycondensation by adding alkylene ether glycol can be mentioned.

As a method for producing polycarbonate using polyalkylene ether glycol as a raw material of the present invention, conventional methods for producing polycarbonate can be employed. For example, as an example of a method for producing a polyether carbonate copolymer, a carbonic acid diester compound, an aliphatic and/or alicyclic diol, and the polyalkylene ether glycol of the present invention are polycondensed by transesterification in the presence of a catalyst. There are several methods. Examples of diester carbonates that can be used include dialkyl carbonates, diaryl carbonates, and alkylene carbonates, which can be obtained by removing from the system monohydroxy compounds, dihydroxy compounds, etc. produced as by-products in the transesterification reaction along with polycondensation. The step of polycondensing a carbonic acid diester compound, an aliphatic and/or alicyclic diol, and the polyalkylene ether glycol of the present invention by transesterification in the presence of a catalyst is carried out in multiple stages using a plurality of reactors. The reaction format may be batchwise, continuously, or a combination of batchwise and continuously.

Further, as a method for producing a polyurethane resin using polyalkylene ether glycol as a raw material according to the present invention, for example, a polyisocyanate component and a diol component can be reacted in one step, or a polyisocyanate component and a diol component can be reacted in advance. It is also possible to prepare a prepolymer and then add a polyisocyanate component or an active hydrogen compound component (polyhydric alcohol, amine compound, etc.) to the prepolymer for reaction. The reaction may be carried out in bulk without using a solvent, and the reaction format may be either batchwise or continuous.

The content of the structural unit derived from the polyalkylene ether glycol of the present invention in the resin obtained using the polyalkylene ether glycol of the present invention as a raw material is preferably 10 to 90% by weight, and 20 to 90% by weight based on the total weight of the resin. It is more preferably 85% by weight, more preferably 30% to 80% by weight.
When the content of the structural unit derived from polyalkylene ether glycol is within the above range, it is easy to obtain a resin that has excellent heat resistance and a good balance between flexibility and melting point.

The 5% weight loss temperature of the resin obtained using the polyalkylene ether glycol of the present invention as a raw material is preferably 380°C or higher, more preferably 385°C or higher, and even more preferably 390°C or higher.
When the 5% weight loss temperature is within the above range, it is easy to obtain a resin with excellent heat resistance.

The reduced viscosity (ηsp/C) of the resin obtained using the polyalkylene ether glycol of the present invention as a raw material is preferably 0.48 dL/g or more, more preferably 0.5 dL/g or more, and even more preferably 0. .6 dL/g or more, particularly preferably 0.7 dL/g or more, most preferably 0.8 dL/g or more. The upper limit of the reduced viscosity is 3.0 dL/g or less, preferably 2.5 dL/g or less, and most preferably 2.0 dL/g or less. If the reduced viscosity is less than 0.48 dL/g, it will not be possible to mold a film or injection molded product, and even if it can be molded, the strength will be insufficient and there is a risk that it will not be usable. Further, if the reduced viscosity is greater than 3.0 dL/g, molding becomes difficult, which is not preferable.
In the present invention, the reduced viscosity (ηsp/C) of the resin was determined from the solution viscosity measured at 30°C at a resin concentration of 0.5 g/dL in phenol/tetrachloroethane (1:1 weight ratio). It is something.

The melting point (Tm1 in the later examples) of the resin obtained using the polyalkylene ether glycol of the present invention as a raw material is preferably -10 to 100°C, more preferably -5 to 95°C, and 0 to 95°C. More preferably, the temperature is 90°C.
When the melting point is within the above range, handling properties are excellent.

The heat of fusion at the melting point derived from the soft segment of the resin obtained using the polyalkylene ether glycol of the present invention as a raw material (corresponding to ΔHm1 in the later examples) is usually about 0 to 50 J/g, and the smaller this value is, the softer it is. Segment components have excellent flexibility and are preferred. Furthermore, the heat of fusion at the melting point of the resin of the present invention (corresponding to ΔHm2 in the later examples) is usually about 0 to 40 J/g, and the smaller this value, the lower the crystallinity of the hard segment and the better the flexibility. It is preferable.

The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples and may be implemented with arbitrary changes within the scope of the gist of the present invention. be able to. In addition, the data in Examples and Comparative Examples were measured by the following method.

< ^1H -NMR analysis>
Using deuterated chloroform as a solvent, ¹ H-NMR was measured using "ECZ-400" manufactured by JEOL Ltd. at a resonance frequency of 400 MHz, a flip angle of 45°, and a measurement temperature of room temperature.

<Measurement of number average molecular weight (1), mass average molecular weight, and molecular weight distribution>
Using GPC (gel permeation chromatography), the number average molecular weight (1), mass average molecular weight, and molecular weight distribution were calculated from a polystyrene calibration curve.
Note that the measurement conditions for GPC were as follows.
Column: TSKgel GMHHR-N (Tosoh, 7.8, 300mm, 9mm) 2 columns Column oven temperature: 40℃
Mobile phase: THF 1mL/min
Analysis time: 30min
Detection: RI detector Sample: 20-50μL injection Calibration method: Polystyrene conversion Calibration curve approximation formula: Cubic formula

<How to calculate the number of hydroxyl groups, terminal esterification rate, terminal olefinization rate, degree of polymerization, and dimer diol content>
The terminal hydroxyl group of the polyalkylene ether glycol reacts with the added acid to become an ester, and also becomes an unsaturated group through an intramolecular dehydration reaction. As a result, in ¹ H-NMR analysis, the signal derived from the methylene group bound to the primary hydroxyl group was around 3.6 ppm, the signal derived from the methylene group bound to the ester group was around 4.0 ppm, and the signal derived from the methylene group bound to the ester group was around 4.0 _ppm . Multiple signals derived from =CH-) are observed around 5.0-6.0 ppm (the solvent is deuterated chloroform). A signal derived from a methylene group bonded to an ether group produced by the desired dehydration condensation reaction is observed at around 3.4 ppm.
The number of hydroxyl groups, the terminal olefinization rate, and the terminal esterification rate were calculated using the following formulas.
Number of hydroxyl groups = [(A/2)/(A/2+B/2+C/3)]×2
Terminal esterification rate = [(B/2)/(A/2+B/2+C/3)]×100
Terminal olefinization rate = [(C/3)/(A/2+B/2+C/3)]×100
Degree of polymerization=D/A+1
Dimer diol content in 1,10-decane diol and dimer diol copolymerized polyalkylene ether glycol = [(E/6)/(A/4+D/4)]×100
(However, in the formula, A is the integral value of the signal derived from the methylene group to which the primary hydroxyl group is bound at around 3.6 ppm; B is the integral value of the signal derived from the methylene group to which the ester group is bound at around 4.0 ppm; C is the integral value of the signal derived from the terminal unsaturated group (CH2=CH-) around 5.0-6.0 ppm, D is the integral value of the signal derived from the methylene group bonded with the ether group around 3.4 ppm, and E is the integral value of the signal derived from the methylene group bonded with the ether group around 3.4 ppm. This is the integral value of the signal derived from the terminal methyl group of the dimer diol around 0.88 ppm.)
For C of the polyalkylene ether glycol containing a dimer diol, the amount of olefin contained in the raw material was corrected using the following formula.
C=C'-Cp/Ap×(A+D)×(dimer diol content in 1,10-decanediol and dimer diol copolymerized polyalkylene ether glycol)
(However, C' is the integral value of the signal derived from the terminal unsaturated group (CH ₂ =CH-) around 5.0-6.0 ppm of the product, and Cp is the integral value of the signal derived from the terminal unsaturated group (CH 2 =CH-) in the vicinity of 5.0-6.0 ppm of the product, and Cp is the integral value of the signal at 5.0-6.0 ppm in the raw material dimer diol. Ap is the integral value of the signal derived from the terminal unsaturated group (CH ₂ = CH-) near 0 ppm, and Ap is the integral value of the signal derived from the methylene group bound to the primary hydroxyl group near 3.6 ppm in the raw material dimer diol. .)

<Toluene concentration measurement>
Based on the integrated value of the signal derived from the methyl group observed around 2.36 ppm (with 1,1,2,2,-tetrachloroethane as the internal standard) in ¹ H-NMR analysis using deuterated chloroform as the solvent. Calculated.

<Moisture concentration measurement>
Coulometric titration using Aquamicron (registered trademark) AKX and Aquamicron (registered trademark) CXU (both manufactured by Mitsubishi Chemical Corporation) with a Karl Fischer moisture analyzer (“CA-200” manufactured by Mitsubishi Chemical Analytic Corporation) It was measured by the method.

<Measurement of hydroxyl value and calculation method of number average molecular weight>
The hydroxyl value of the polyalkylene ether glycol composition was measured using an automatic titrator ("GT-200" manufactured by Mitsubishi Chemical Analytech) in accordance with ASTM E-1899-16.
From the measured hydroxyl value, the number average molecular weight (Mn) was determined using the following formula (I).
Number average molecular weight = 2 x 56.1/(hydroxyl value x ^10-3 )...(I)

<TG-DTA, measurement of 5% weight loss temperature>
Using Hitachi High-Tech Science's differential thermogravimetry simultaneous measurement device "STA200RV", approximately 7 mg of the sample was placed on an aluminum container and heated from 30 to 500°C at a heating rate of 10°C/min in a nitrogen atmosphere (nitrogen flow rate 200ml/min). The mass of the sample was measured up to ℃. The temperature at the time of 5% weight loss was defined as the 5% weight loss temperature (unit: °C). The 5% weight loss temperature is an index of heat resistance, and the higher the temperature, the higher the heat resistance.

<Yellowness (YI)>
The yellowness of the test piece (thickness: 4 mm) was measured using a spectrophotometer (model name: U4100, manufactured by Hitachi High-Technologies Corporation) and a C light source in accordance with ISO17223. Using three test pieces, each test piece was measured once, and the average value was taken as yellowness index (YI).

<Measurement of number of colors>
The color number of the dimer diol and polyalkylene ether glycol composition was measured using a cross-photometric color difference meter (Nippon Denshoku Kogyo Co., Ltd. "ZE-2000"). Color numbers were measured as APHA values (Platinum-Cobalt System) according to American Society for Testing and Materials (ASTM) D-1209. As the standard solution for APHA500, Hazen colorimetric stock solution (No. 500) manufactured by Hayashi Pure Chemical Industries, Ltd. was used.

<Measurement of melting point 1, ΔHm1, melting point 2, ΔHm2 by DSC>
The melting point (Tm, unit: °C) was measured using a differential scanning calorimeter "DSC7000x" manufactured by Hitachi High-Tech Science. The temperature increase rate is 10°C/min, and the lower one of the maximum peak vertices is Tm1 (melting point derived from the soft segment), the higher one is Tm2 (melting point of the polymer), and the respective peak areas are the heats of fusion ΔHm1, ΔHm2 ( mJ/mg). The smaller the value of ΔHm, the lower the crystallinity.

<Measurement of reduced viscosity (ηsp/C)>
The polyester resins obtained in the production examples and comparative production examples were measured at 30°C for solutions at a concentration of 0.5 g/dl in phenol/1,1,2,2-tetrachloroethane (1:1 weight ratio). The reduced viscosity (ηsp/C) was determined from the solution viscosity.

<Measurement of tensile modulus, breaking strength, and breaking elongation rate by tensile test>
Using the polyester resins obtained in the production examples and comparative production examples, heat pressing was performed at 240°C using a tabletop heat press machine to create a press film with a thickness of 200 μm. A dumbbell-shaped sample was punched out from the obtained press film, and a tensile test was conducted according to JIS K7127 to measure the tensile modulus, strength at break, and elongation at break.

<Synthetic material of polyalkylene ether glycol>
・Dimer diol: Croda Japan Co., Ltd. Product name “Pripol 2033”
・1,10-Decanediol: Tokyo Chemical Industry Co., Ltd. or Toyokuni Oil Co., Ltd. ・Trifluoromethanesulfonic acid: Tokyo Chemical Industry Co., Ltd. ・p-Toluenesulfonic acid monohydrate: Fujifilm Wako Pure Chemical Industries, Ltd.

[Example 1]
<Production example of dimer diol oligomer Mn1000>
535.3 g (0.998 mol) of dimer diol (Pripol 2033 manufactured by Croda Japan Co., Ltd.) was placed in a four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer, and heated to 50°C in an oil bath. After heating, the inside of the reactor was degassed under reduced pressure and replaced with nitrogen. While supplying nitrogen at a rate of 0.20 NL/min, 2.69 g (17.9 mmol) of trifluoromethanesulfonic acid was slowly added while maintaining the temperature at 50°C. This flask was heated by immersing it in an oil bath, and the temperature of the liquid in the flask reached 150° C. in about 0.5 to 1 hour. The reaction was started when the temperature of the liquid in the flask reached 150°C, and thereafter, the reaction was carried out for 2.5 hours while maintaining the liquid temperature at 148 to 152°C. The water produced by the reaction was distilled off along with nitrogen.
The reaction product was allowed to cool to around 120°C, and 150g of ion-exchanged water was poured into it. The mixture was stirred at 90° C. for about 10 to 30 minutes, left to stand for 10 minutes to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated seven times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, 100 mL of toluene was poured, and toluene was distilled off under reduced pressure at 60° C. and 180 torr for azeotropic dehydration. Thereafter, 100 mL of toluene was poured, and the toluene was distilled off under reduced pressure at 70° C. and 70 torr. The water content was measured, and azeotropic dehydration was repeated a total of 5 times until the water concentration reached 300 ppm or less. The temperature of the oil bath was raised to 100° C., and the mixture was devolatilized under reduced pressure using an oil rotary vacuum pump for 4 hours until the toluene concentration reached 0.1% by weight or less to obtain the desired polyalkylene ether glycol.
The degree of polymerization determined by NMR was 1.43, the terminal olefinization rate was 0.69 mol%, and the terminal esterification rate was below the NMR detection limit. The number average molecular weight determined by GPC was 967, the mass average molecular weight was 1268, and the molecular weight distribution was 1.31. The hydroxyl value was 145.7, and the number average molecular weight calculated from this was 770. The APHA value determined by a color difference meter was 59. The 5% weight loss temperature was 313.3°C.

[Example 2]
<110-decanediol/Pripol 2033 (75/25) Mn1000 production example>
128 g (0.736 mol) of 1,10-decanediol and 132 g (0.245 mol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked tube equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer. After charging the mixture into a flask and heating and melting it in an oil bath, the inside of the reactor was degassed under reduced pressure and replaced with nitrogen. The flask was heated by immersing it in an oil bath while supplying nitrogen at a rate of 0.20 NL/min, and when the temperature exceeded 160°C, 5.73 g (30.1 mmol) of p-toluenesulfonic acid monohydrate was added slowly. added something. The reaction was started when the temperature of the liquid in the flask reached 170°C, and thereafter, the reaction was carried out for 13 hours while maintaining the liquid temperature at 170 to 171°C. The water produced by the reaction was distilled off along with nitrogen. 37 g of a 10% by weight aqueous sodium hydroxide solution was poured into the reaction solution that had been allowed to cool to around 90°C, and the mixture was heated under reflux at 110°C for 15 hours to hydrolyze the ester.
The reaction product was heated to around 90°C, and 500g of ion-exchanged water was poured into it. The mixture was stirred at 90° C. for about 15 to 30 minutes, left to stand for 1 to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated eight times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, 100 mL of toluene was poured, and toluene was distilled off under reduced pressure at 100° C. and 20 torr for azeotropic dehydration. The water content was measured, and azeotropic dehydration was repeated a total of 5 times until the water concentration reached 300 ppm or less. The temperature of the oil bath was raised to 120° C., and the mixture was devolatilized under reduced pressure using an oil rotary vacuum pump for 1 hour until the toluene concentration reached 0.1% by weight or less to obtain the desired polyalkylene ether glycol.
The polymerization degree determined by NMR was 3.71, the dimer diol content in the polyalkylene ether glycol was 26.6 mol%, the terminal olefinization rate was 0.67 mol%, and the terminal esterification rate was below the NMR detection limit. Ta. The number average molecular weight determined by GPC was 956, the mass average molecular weight was 2001, and the molecular weight distribution was 2.09. The hydroxyl value was 121.0, and the number average molecular weight calculated from this was 927. The 5% weight loss temperature was 284.9°C.

[Example 3]
<110-decanediol/Pripol 2033 (75/25) Mn2000 production example>
247 g (1.415 mol) of 1,10-decanediol and 253 g (0.472 mol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked tube equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer. After charging the mixture into a flask and heating and melting it in an oil bath, the inside of the reactor was degassed under reduced pressure and replaced with nitrogen. The flask was heated by immersing it in an oil bath while supplying nitrogen at a rate of 0.20 NL/min, and when the temperature exceeded 100°C, 5.01 g (33.4 mmol) of trifluoromethanesulfonic acid and 2.0 g of ion-exchanged water were slowly added. 50g of the mixture was added. This flask was immersed in an oil bath and heated, and the temperature of the liquid in the flask reached 150° C. in about 0.5 hours. The reaction was started when the temperature of the liquid in the flask reached 150°C, and thereafter, the reaction was carried out for 8.75 hours while maintaining the liquid temperature at 149 to 151°C. The water produced by the reaction was distilled off along with nitrogen.
The reaction product was allowed to cool to around 120°C, and 300g of ion-exchanged water was poured into it. The mixture was stirred at 90° C. for about 10 to 30 minutes, left to stand for 10 minutes to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated 29 times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, 300 mL of toluene was poured, and toluene was distilled off under reduced pressure at 100° C. and 20 torr for azeotropic dehydration. Next, 100 mL of toluene was poured, the water content was measured, and azeotropic dehydration was repeated a total of four times until the water concentration reached 300 ppm or less. The temperature of the oil bath was raised to 120° C., and the mixture was devolatilized under reduced pressure using an oil rotary vacuum pump for 2 hours until the toluene concentration reached 0.1% by weight or less to obtain the desired polyalkylene ether glycol.
The polymerization degree determined by NMR was 8.68, the dimer diol content in the polyalkylene ether glycol was 25.2 mol%, the terminal olefinization rate was 2.11 mol%, and the terminal esterification rate was below the NMR detection limit. Ta. The number average molecular weight determined by GPC was 2441, the mass average molecular weight was 5232, and the molecular weight distribution was 2.14. The hydroxyl value was 54.7, and the number average molecular weight calculated from this was 2,052. The 5% weight loss temperature was 371.6°C.

[Example 4]
<110-decanediol/Pripol 2033 (90/10) Mn1000 production example>
373 g (2.137 mol) of 1,10-decanediol and 128 g (0.237 mol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked tube equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer. After charging the mixture into a flask and heating and melting it in an oil bath, the inside of the reactor was degassed under reduced pressure and replaced with nitrogen. The flask was heated by immersing it in an oil bath while supplying nitrogen at a rate of 1.0 NL/min, and when the temperature exceeded 147°C, 5.03 g (33.5 mmol) of trifluoromethanesulfonic acid and 2.0 g of ion-exchanged water were slowly added. 51 g of the mixture was added to start the reaction. Thereafter, the temperature of the solution was maintained at 149 to 151°C and the reaction was carried out for 6 hours. After cooling to room temperature, the temperature was raised again and the reaction was carried out for 15 minutes at a liquid temperature of 130°C. The water produced by the reaction was distilled off along with nitrogen.
The reaction product was allowed to cool to around 90°C, and 300g of ion-exchanged water was poured into it. The mixture was stirred at 90° C. for about 15 to 30 minutes, left to stand for 0.5 to 1 hour, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated eight times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, 300 mL of toluene was poured, and toluene was distilled off under reduced pressure at 100° C. and 20 torr for azeotropic dehydration. Next, 200 mL of toluene was poured, and azeotropic dehydration was carried out at 100° C. and 10 torr. After this, 100 mL of toluene was poured, the water content was measured, and azeotropic dehydration was repeated a total of 5 times until the water concentration reached 300 ppm or less. The temperature of the oil bath was raised to 120° C., and the mixture was devolatilized under reduced pressure using an oil rotary vacuum pump for 2 hours until the toluene concentration reached 0.1% by weight or less to obtain the target polyalkylene ether glycol.
The degree of polymerization determined by NMR was 4.88, the dimer diol content in the polyalkylene ether glycol was 10.2 mol%, the terminal olefinization rate was 0.93 mol%, and the terminal esterification rate was below the NMR detection limit. Ta. The number average molecular weight determined by GPC was 969, the mass average molecular weight was 2304, and the molecular weight distribution was 2.38. The hydroxyl value was 122.6, and the number average molecular weight calculated from this was 915. The 5% weight loss temperature was 271.9°C.

[Example 5]
<110-decanediol/Pripol 2033 (90/10) Mn2000 production example>
373 g (2.138 mol) of 1,10-decanediol and 128 g (0.238 mol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) were placed in a four-necked tube equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer. After charging the mixture into a flask and heating and melting it in an oil bath, the inside of the reactor was degassed under reduced pressure and replaced with nitrogen. The flask was heated by immersing it in an oil bath while supplying nitrogen at a rate of 0.20 NL/min, and when the temperature exceeded 100°C, 5.03 g (33.5 mmol) of trifluoromethanesulfonic acid and 2.0 g of ion-exchanged water were slowly added. 48g of the mixture was added. This flask was immersed in an oil bath and heated, and the temperature of the liquid in the flask reached 150° C. in about 0.5 hours. The reaction was started when the temperature of the liquid in the flask reached 150°C, and thereafter, the reaction was carried out for 10.5 hours while maintaining the liquid temperature at 149 to 151°C. The water produced by the reaction was distilled off along with nitrogen.
The reaction product was allowed to cool to around 120°C, and 300g of ion-exchanged water was poured into it. The mixture was stirred at 90° C. for about 10 to 30 minutes, left to stand for 10 minutes to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated 25 times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, 300 mL of toluene was poured, and toluene was distilled off under reduced pressure at 100° C. and 20 torr for azeotropic dehydration. Next, 200 mL of toluene was poured, and azeotropic dehydration was performed at 100° C. and 20 torr. After this, 100 mL of toluene was poured, the water content was measured, and azeotropic dehydration was repeated a total of 5 times until the water concentration reached 300 ppm or less. The temperature of the oil bath was raised to 120° C., and the mixture was devolatilized under reduced pressure using an oil rotary vacuum pump for 1.5 hours until the toluene concentration reached 0.1% by weight or less to obtain the desired polyalkylene ether glycol.
The polymerization degree determined by NMR was 10.50, the dimer diol content in the polyalkylene ether glycol was 10.3 mol%, the terminal olefinization rate was 2.74 mol%, and the terminal esterification rate was below the NMR detection limit. Ta. The number average molecular weight determined by GPC was 2366, the mass average molecular weight was 5429, and the molecular weight distribution was 2.29. The hydroxyl value was 56.9, and the number average molecular weight calculated from this was 1970. The 5% weight loss temperature was 368.9°C.

[Comparative example 1]
<PDMG Mn1000 production example>
・Polymerization process, ester decomposition process 9.00 kg (5.16 mol) of 1,10-decanediol was supplied with nitrogen at a rate of 1.0 NL/min to a four-necked flask equipped with a distillation tube, nitrogen introduction tube, thermocouple, and stirrer. I prepared it while doing so. While stirring, 0.198 kg (1.04 mol) of p-toluenesulfonic acid monohydrate was slowly added. This flask was heated by immersing it in an oil bath, and the temperature of the liquid in the flask reached 170° C. in about 0.5 to 1 hour. The reaction was started when the temperature of the liquid in the flask reached 170°C, and thereafter, the reaction was carried out for 18 hours while maintaining the liquid temperature at 168 to 172°C. The water produced by the reaction was distilled off along with nitrogen. 0.90 kg of 10% by weight aqueous sodium hydroxide solution was poured into the reaction solution that was allowed to cool to around 90°C, and the mixture was heated under reflux at 110°C for 20 hours to hydrolyze the ester.
- Water washing step, drying step The polymerization step and the ester decomposition step were carried out in two batches, and after cooling to around 90° C., the products of the two batches were mixed. 36 kg of ion-exchanged water heated to 80°C or higher was poured. The mixture was stirred at 80° C. for about 15 minutes, left to stand for 1 to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated 10 times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, it was dried under reduced pressure at 40°C to obtain the target polydecamethylene ether glycol.
The degree of polymerization determined by NMR is 5.51, the number average molecular weight determined by GPC is 1210, the mass average molecular weight is 2413, the molecular weight distribution is 1.99, the terminal olefin conversion rate determined by NMR is 0.68 mol%, terminal ester The conversion rate was below the NMR detection limit. The hydroxyl value was 134.4, and the number average molecular weight calculated from this was 835. The 5% weight loss temperature was 259.8°C.

[Comparative example 2]
<PDMG Mn2000 production example>
450 g (2.58 mol) of 1,10-decanediol was charged into a four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermocouple, and a stirrer while supplying nitrogen at a rate of 0.2 NL/min. 9.07 g (60.4 mmol) of trifluoromethanesulfonic acid was slowly added while stirring. This flask was heated by immersing it in an oil bath, and the temperature of the liquid in the flask reached 150° C. in about 0.5 to 1 hour. The reaction was started when the temperature of the liquid in the flask reached 150°C, and thereafter, the reaction was carried out for 7.5 hours while maintaining the liquid temperature at 149 to 150°C. The water produced by the reaction was distilled off along with nitrogen. 36 kg of ion-exchanged water heated to 80°C or higher was poured into the reaction solution that had been allowed to cool to around 90°C. The mixture was stirred at 80° C. for about 15 minutes, left to stand for 1 to 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was extracted. The electrical conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil/water separation were repeated 40 times in total until the electrical conductivity reached 0 to 10 μS/cm. After taking out the oil layer, it was dried under reduced pressure at 40°C to obtain the target polydecamethylene ether glycol.
The degree of polymerization determined by NMR is 14.08, the number average molecular weight determined by GPC is 2855, the mass average molecular weight is 6231, the molecular weight distribution is 2.18, the terminal olefin conversion rate determined by NMR is 2.68 mol%, terminal ester The conversion rate was below the NMR detection limit. The hydroxyl value was 55.9, and the number average molecular weight calculated from this was 2009. The 5% weight loss temperature was 325.6°C.

The results obtained are shown in Table 1.
In Table 1, the number average molecular weight (1) is the number average molecular weight determined by GPC, and the number average molecular weight (2) is the number average molecular weight calculated from the hydroxyl value.

As shown in Table 1, the polyalkylene ether glycols of Examples 1 to 5 to which the present invention was applied had excellent heat resistance and a high number of hydroxyl groups.
In formula (1), the polyalkylene ether glycol of Comparative Example 1 in which n/(n+m) is less than 0.1 and the number average molecular weight is 835 has n/(n+m) in heat resistance and hydroxyl value. was 0.1 or more, and was inferior to Examples 1, 2, and 4, in which the number average molecular weight was 770 to 927.
In formula (1), the polyalkylene ether glycol of Comparative Example 2, in which n/(n+m) is less than 0.1 and the number average molecular weight is 2009, has n/(n+m) of 0 in heat resistance and hydroxyl groups. .1, and was inferior to Examples 3 and 5, which had a number average molecular weight of 1970 to 2052.

[Example 6]
28.2 g (52.6 mmol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) was placed in a 50 mL vial, and nitrogen substitution was performed by bubbling nitrogen. Thereafter, while nitrogen was flowing through the liquid, a mixture of 0.28 g (1.86 mmol, 1% by weight based on the dimer diol) of trifluoromethanesulfonic acid and 0.14 g of ion-exchanged water was slowly added. After stirring for 1 hour at room temperature in a nitrogen atmosphere, yellowness index (YI) and color number (APHA value) were measured.

[Example 7]
29.7 g (55.4 mmol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) was placed in a 50 mL vial, and nitrogen substitution was performed by bubbling nitrogen. Thereafter, while nitrogen was flowing through the liquid, a mixture of 0.27 g (1.80 mmol, 1% by weight based on the dimer diol) of trifluoromethanesulfonic acid and 0.06 g of ion-exchanged water was slowly added. The vial was capped and stirred for 1 hour in a sealed state. After stirring for 1 hour at room temperature in a nitrogen atmosphere, yellowness index (YI) and color number (APHA value) were measured.

[Comparative example 3]
31.6 g (59.0 mmol) of dimer diol (Pripol 2033, manufactured by Croda Japan Co., Ltd.) was placed in a 50 mL vial, and nitrogen substitution was performed by bubbling nitrogen. Thereafter, while nitrogen was flowing through the liquid, 0.32 g (2.15 mmol, 1% by weight based on the dimer diol) of trifluoromethanesulfonic acid was slowly added. After stirring for 1 hour at room temperature in a nitrogen atmosphere, yellowness index (YI) and color number (APHA value) were measured.

The yellowness index (YI) and color number (APHA value) of the obtained reaction solution were measured. The results obtained are shown in Table 2.

As shown in Table 2, Examples 6 and 7 in which the concentration of the acid catalyst aqueous solution was 90% by mass or less were able to suppress coloring upon addition of acid.
In Comparative Example 3 in which the concentration of the acid catalyst aqueous solution was more than 90% by mass, coloring of the obtained polyalkylene ether glycol could not be suppressed.

<Production method of polyalkylene ether glycol copolyester polyester>
A polyester resin (terephthalic acid/butanediol/polyalkylene glycol copolyester) was produced using the polyalkylene ether glycol obtained in Examples and Comparative Examples as a raw material, and its physical properties were measured.

[Manufacture example 1]
<PBT-(1,10-decanediol/Pripol 2033=75/25 Mn=1000) 70% by weight production example>
In a reaction vessel equipped with a stirring device, a nitrogen inlet, a heating device, a thermometer, and a pressure reduction port, as raw materials, 26.45 parts by weight of dimethyl terephthalic acid, 9.18 parts by weight of 1,4-butanediol, and the mixture in Example 2 were added. 70.00 parts by weight of the obtained polyalkylene ether glycol (1,10-decanediol) and 0.71 parts by weight of a 1,4-butanediol solution in which 6.0% by weight of titanium tetrabutyrate had been dissolved in advance were charged. .
While the contents of the container were being stirred, nitrogen gas was introduced into the container, and the inside of the system was made into a nitrogen atmosphere by vacuum displacement. Next, the system was heated to 150°C for 1 hour while stirring, and then raised to 210°C for 1 hour and 45 minutes, and reacted at this temperature for 15 minutes. Next, after adding 0.36 parts by weight of a 1,4-butanediol solution in which 6.0% by weight of titanium tetrabutyrate was dissolved in advance, the pressure was adjusted to 0.05×103 Pa or less over 1 hour and 30 minutes. The pressure was reduced. 15 minutes after the start of depressurization, the temperature was raised to 240°C over 45 minutes, and polymerization was continued for 4 hours and 15 minutes while maintaining the heated and depressurized state at 240°C. / polyalkylene glycol copolymerized polyester) was obtained.

[Production example 2]
<Production example of PBT-dimer diol oligomer Mn=1000 70% by weight>
The polyalkylene ether glycol (1,10-decanediol) obtained in Example 1 was used, and the raw materials and catalyst were charged in the same manner as in Production Example 1, a polycondensation reaction was carried out, and the target viscosity was reached. By the way, the same procedure as Production Example 1 was carried out except that the polycondensation reaction was stopped.

[Comparative production example 1]
<PBT-PDMG 70% by weight production example>
The same procedure as in Production Example 1 was used except that 70.00 parts by weight of polydecamethylene ether glycol was used instead of 70.00 parts by weight of polyalkylene ether glycol (1,10-decanediol) obtained in Example 2. A condensation reaction was performed.

Reduced viscosity, melting point (Tm), heat of fusion (ΔHm), thermal decomposition temperature (Td5: 5% weight loss temperature), tensile test (tensile modulus, breaking strength, Table 3 shows the results of the elongation at break) and elastomer properties.
In Table 3, "DMT" represents dimethyl terephthalic acid, and "1,4-BG" represents 1,4-butanediol.

Claims (7)

A polyalkylene ether glycol represented by the following formula (1).
HO-(R ¹ -O) _n -(R ² -O) _m -H...(1)
(In formula (1), R ¹ is a divalent diol derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a hydrocarbon group, ^R2 represents an alkylene group having 2 to 18 carbon atoms, n and m each independently represent a real number of 0 or more, and n/(n+m) is 0.1 or more.) The polyalkylene ether glycol according to claim 1, wherein n/(n+m) in the formula (1) is 0.25 or more. The polyalkylene ether glycol according to claim 1 or 2, which has a number average molecular weight calculated from a hydroxyl value of 300 to 5,000. The polyalkylene ether glycol according to any one of claims 1 to 3, having a molecular weight distribution of 1.1 to 3.0. The polyalkylene ether glycol according to any one of claims 1 to 4, wherein in the formula (1), R ² is a 1,10-decylene group. A method for producing polyalkylene ether glycol, comprising a step of dehydrating and condensing a glycol component using an acid catalyst,
A method for producing polyalkylene ether glycol, wherein in the dehydration condensation step, an aqueous acid catalyst solution having a concentration of 70% by weight or less is used as the acid catalyst. The method for producing polyalkylene ether glycol according to claim 6, wherein the polyalkylene ether glycol is represented by the following formula (1).
HO-(R ¹ -O) _n -(R ² -O) _m -H...(1)
(In formula (1), R ¹ is a divalent diol derived from a dimer diol having 36 to 44 carbon atoms obtained by reducing a cyclic or acyclic dimer acid that is a dimer of unsaturated fatty acids. represents a hydrocarbon group, ^R2 represents an alkylene group having 2 to 18 carbon atoms, and n and m each independently represent a real number of 0 or more.)