JP2019108418A - Polyalkylene ether glycol composition and method for producing the same - Google Patents

Abstract

To provide a polyalkylene ether glycol composition which has higher thermal stability as compared with conventional polyalkylene ether glycols and is capable of suppressing catalyst poisoning in a post-process.SOLUTION: The polyalkylene ether glycol composition contains a nitrogen-containing compound. The content of the nitrogen-containing compound with respect to a polyalkylene ether glycol is 0.1 mass ppm or more and 40 mass ppm or less as a concentration in terms of nitrogen atoms. There is also provided a method for producing the polyalkylene ether glycol composition through a purification step of reducing an acetal contained in a polyalkylene ether glycol composition.SELECTED DRAWING: None

Description

  The present invention relates to a polyalkylene ether glycol composition as a raw material for polyurethane, polyurethaneurea, polyester and the like, and a method for producing the same.

  Polyalkylene ether glycols, among which polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG) are used as raw materials for polyesters such as thermosetting polyurethanes, thermoplastic polyurethanes, polyurethaneureas, thermoplastic elastomers, etc. .

  As a method for producing PTMG, for example, polytetramethylene ether which is a polytetramethylene ether glycol diester by ring-opening polymerization of tetrahydrofuran with acetic anhydride in the presence of a solid acid catalyst comprising a composite metal oxide such as silica-alumina There is known a method of producing glycol diacetic acid ester (hereinafter sometimes abbreviated as PTME) and then hydrolyzing or transesterification with a lower alcohol in the presence of an alkali catalyst to produce PTMG (Patent Document 1) 1).

  Further, as a method of improving the hue in PTMG, a method of hydrogenation with a heterogeneous catalyst is known, and by hydrogenation, an acetal which is a causative substance of coloring is decomposed and removed (Patent Document 2).

Unexamined-Japanese-Patent No. 4-306228 Japanese Patent Publication No. 2004-506763

  However, in the previously known color improvement method, polyalkylene ether glycol is easily decomposed, the monomers constituting the polyalkylene ether glycol are separated, and the catalyst does not function well and is efficiently performed. There is a problem that the acetal number can not be reduced.

  This invention is made in view of the said subject, Comprising: Thermal stability is favorable and it aims at providing the polyalkylene ether glycol composition which is excellent in acetal number reduction efficiency.

In order to solve the above problems, the inventors of the present invention have a trace amount of acid and peroxide which can not be removed by conventional purification techniques in polyalkylene ether glycol, which causes acid catalyzed reaction and radical cleavage, As a result of repeated investigations based on the assumption that the polyalkylene ether glycol of part is converted to cyclic ether, nitrogen-containing compounds conventionally considered to be the causative agents of catalyst deterioration, in particular certain structures among them, By including the nitrogen-containing compound having a specific concentration in a specific concentration range, it is possible to suppress catalyst deterioration when hydrogenating acetal, and to suppress conversion of polyalkylene ether glycol to cyclic ether, As a result, the thermal stability and catalyst life of polyalkylene ether glycol during acetal hydrogenation can be significantly improved. Heading, which resulted in the completion of the present invention.
The present invention has been achieved based on such findings, and the gist of the following [1] to [16].

[1] A polyalkylene ether glycol composition containing a nitrogen-containing compound, wherein the content of the nitrogen-containing compound is 0.1 mass ppm or more and 40 mass ppm or less as the nitrogen atom conversion concentration with respect to the polyalkylene ether glycol Certain polyalkylene ether glycol compositions.
[2] The polyalkylene ether glycol composition according to [1], wherein the nitrogen-containing compound is at least one of an amine and an amide.
[3] The polyalkylene ether glycol composition according to [1] or [2], wherein the boiling point of the nitrogen-containing compound is -40 ° C or more and 120 ° C or less.
[4] The polyalkylene ether glycol composition according to any one of [1] to [3], wherein the nitrogen-containing compound is an amine containing two or more N atoms.
[5] The polyalkylene ether glycol composition according to any one of [1] to [4], wherein the nitrogen-containing compound is an anion exchange resin eluate.
[6] The polyalkylene ether glycol composition according to any one of [1] to [5], wherein the molecular weight of the nitrogen-containing compound is 17 or more and 500 or less.
[7] The polyalkylene ether glycol composition further contains tetrohydrofuran, and the content of the tetrahydrofuran is 5 mass ppm or more and 200 mass ppm or less with respect to the polyalkylene ether glycol [1] to [6] The polyalkylene glycol composition as described in any one of the above.
[8] The polyalkylene ether glycol composition according to any one of [1] to [7], which has an acetal number of 0.01 mg-KOH / g or more and 3.0 mg-KOH / g or less.
[9] to any one of the peroxide concentration is _{0.01μg-H 2 O 2} / g or more _{3.0μg-H 2 O 2} / g or less with respect to polyalkylene ether glycol [1] to [8] Polyalkylene ether glycol composition as described.
[10] The polyalkylene ether glycol composition according to any one of [1] to [9], wherein the antioxidant concentration is 10 mass ppm or more and 1000 mass ppm or less with respect to the polyalkylene ether glycol.
[11] A method for producing the polyalkylene ether glycol composition according to any one of [1] to [10], comprising a purification step of reducing an acetal contained in the polyalkylene ether glycol composition. Method of producing a glycol composition.
[12] The method for producing a polyalkylene ether glycol composition according to [11], wherein the acetal contained in the polyalkylene ether glycol composition is reduced by a solid catalyst in the purification step.
[13] An elastic stretchable fiber using the polyalkylene ether glycol composition according to any one of [1] to [10].
[14] A polyurethane using the polyalkylene ether glycol composition according to any one of [1] to [10].
[15] A synthetic leather using the polyalkylene ether glycol composition according to any one of [1] to [10].
[16] A thermoplastic elastomer using the polyalkylene ether glycol composition according to any one of [1] to [10].

  The polyalkylene ether glycol composition of the present invention has high thermal stability, and can suppress catalyst deterioration at the time of acetal hydrogenation, and can suppress catalyst poisoning in subsequent steps even when used as a raw material for various derivatives. .

  The present invention will be described in detail below, but the present invention is not limited to the embodiments described below as long as the scope of the present invention is not exceeded.

[Polyalkylene ether glycol composition]
The polyalkylene ether glycol composition of the present invention contains the nitrogen-containing compound in an amount of 0.1 mass ppm or more and 40 mass ppm or less in terms of nitrogen atom relative to the polyalkylene ether glycol.

  The polyalkylene ether glycol composition of the present invention contains the nitrogen-containing compound at the above-described nitrogen atom equivalent concentration, and as described later, cyclics such as acetal and peroxide as impurities, and tetrachlorohydrofuran as unreacted raw material. Although it contains additives such as ether and antioxidants added for the purpose of preventing oxidation if necessary, and may or may not contain a solvent, it is not a solvent. The content of polytetramethylene ether glycol in the solid content of the composition is 5% by mass or more, and the nitrogen-containing compound content, the following acetal value, the concentration of tetrohydrofuran, the concentration of antioxidant, the concentration of peroxide , Concentration relative to polyalkylene ether glycol.

The polyalkylene ether glycol is a straight chain having primary hydroxyl groups at both ends represented by the general formula HO-[(CH ₂ ) _n O] _m -H (m is an integer of 2 or more and n is an integer of 1 or more). Polyether glycol, which is generally prepared from polytetramethylene ether glycol diester obtained by ring-opening polymerization of cyclic ether as described later.

The molecular weight of the polyalkylene ether glycol contained in the polyalkylene ether glycol composition of the present invention is not particularly limited, but the number average molecular weight (Mn) is 250 to 4500, particularly 650 to 3000, in various applications. preferable. The molecular weight of polytetramethylene ether glycol can be adjusted by controlling the ring-opening polymerization reaction temperature and the quantitative ratio of the amount of carboxylic acid anhydride to cyclic ether in the method for producing polytetramethylene ether glycol described later.
The molecular weight distribution (Mw / Mn) of the polyalkylene ether glycol is usually 1 or more, preferably 1.2 or more, more preferably 1.5 or more, and the upper limit is usually 3 or less, preferably 2.5 or less And more preferably 2.2 or less.
Here, the number average molecular weight (Mn) of polytetramethylene ether glycol is measured by the method described in the section of the examples described later. The same applies to the molecular weight distribution (Mw / Mn).

  In the polyalkylene ether glycol composition of the present invention, the nitrogen atom-equivalent concentration of the nitrogen-containing compound to the polyalkylene ether glycol is usually 0.1 mass ppm or more, preferably 0.5 mass ppm or more, more preferably 1.0 mass ppm The upper limit is usually 40 mass ppm or less, preferably 25 mass ppm or less, more preferably 15 mass ppm or less. If the nitrogen atom equivalent concentration of the nitrogen-containing compound is too low, it becomes thermally unstable and tends to generate cyclic ether and the like by decomposition of polyalkylene ether glycol, and in particular, the vacuum degree of the distillation column is increased when purifying polyalkylene ether glycol. It tends to deteriorate or to deteriorate the quality by increasing cyclic ether in the hydrogenation reaction. On the other hand, even if the nitrogen atom conversion concentration of the nitrogen-containing compound is too high, cyclic ether and the like are easily generated, and poisoning of the hydrogenation catalyst described later and coloring and urethane reaction rate at the time of producing polyurethane from polyalkylene ether glycol It is easy to cause problems such as difficulty in control.

  The nitrogen-containing compound contained in the polyalkylene ether glycol composition of the present invention is preferably at least one of an amine and an amide.

  As an amine, Preferably, the amine shown by following formula (1) (Hereinafter, it may be called "amine (1).") Is mentioned.

In the above formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group (including an aryloxy group), a hydroxy group, an amino group or an alkylthio group. Or an arylthio group, which may further have a substituent, and the substituent may contain a hetero atom. R ^{1 to} R ³ may be the same or different. In the present invention, the amine also includes ammonia in which all of R ^{1 to} R ³ in the above formula (1) are hydrogen atoms.

Each of R ^{1 to} R ³ is preferably independently a hydrogen atom, an alkyl group, an aryl group or an amino group from the viewpoint of improving the basicity.

The alkyl group of R ^{1 to} R ³ is a chain (linear or branched) alkyl group or a cyclic alkyl group, and in the case of a chain alkyl group, usually 1 to 20 carbon atoms, preferably 1 to 12 It is. Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, An octyl group, a decyl group, etc. are mentioned. In the case of a cyclic alkyl group, it is usually 3 to 20 carbon atoms, preferably 4 to 11 carbon atoms. Specific examples thereof include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. The substituent which the alkyl group may have is not particularly limited as long as it does not significantly inhibit the effects of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

The alkenyl group of R ^{1 to} R ³ is a chain (straight or branched) alkenyl group or a cyclic alkenyl group, and in the case of a chain alkenyl group, usually 2 to 20 carbon atoms, preferably 2 to 12 Specific examples thereof include ethenyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group and the like. Moreover, in the case of a cyclic alkenyl group, it is a C3-C20 normally, Preferably it is 4-11, A cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group etc. are mentioned as the specific example. The substituent which the alkenyl group may have is not particularly limited as long as it does not significantly impair the effects of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group, and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

The aryl group of R ^{1 to} R ³ usually has 5 to 20 carbon atoms, preferably 5 to 12 carbon atoms, and may be an aromatic hydrocarbon group, and may be a heteroatom such as oxygen, nitrogen or sulfur. It may be an aromatic heterocyclic group (heteroaryl group) contained. The substituent which the aryl group may have is not particularly limited as long as it does not significantly impair the effect of the present invention, but a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms 10 acyl group, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, 7 carbon atoms And alkylaryl groups having 12 to 12 carbon atoms, arylaryl groups having 7 to 12 carbon atoms, arylalkyl groups having 7 to 12 carbon atoms, arylalkoxy groups having 7 to 12 carbon atoms, and hydroxy groups. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be further contained in this substituent.

  Specific examples of the aryl group include phenyl group, benzyl group, mesityl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4- Dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl Group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group Group, 4-trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group Group, 3,5-dimethoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-aminophenyl group, trifluoromethylphenyl group, pentafluorophenyl group, isoxazolyl group, isothiazolyl group, imidazolyl group, oxazolyl Group, thiazolyl group, thiadiazolyl group, thienyl group, thiophenyl group, triazolyl group, tetrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrazolyl group, pyrrolyl group, pyranyl group, furyl group, furazanyl group, imidazolidinyl group, Isoquinolyl group, isoindolyl group, indolyl group, quinolyl group, pyridothiazolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, benzofuranyl group, imidazopyridinyl group Triazolium pyridinylalkyl group, purinyl group and the like.

As an alkoxy group (an aryloxy group is included) of R < ¹ > -R < ³ >, it is C1-C20 normally, Preferably it is 1-12. Specific examples thereof include a methoxy group, an ethoxy group, a butoxy group and a phenoxy group. The substituent which the alkoxy group may have is not particularly limited as long as it does not significantly inhibit the effect of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

The amino group of R ^{1 to} R ³ is usually 0 to 20, preferably 0 to 12 carbon atoms. Specific examples thereof include methylamino, ethylamino, propylamino, butylamino, dimethylamino, diethylamino, diethylamino, anilino, toluidino, anisidino, diphenylamino, N-methyl-N-phenylamino Groups and the like. The substituent which the amino group may have is not particularly limited as long as it does not significantly inhibit the effect of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

The alkylthio group as R ^{1 to} R ³ generally has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group and the like. The substituent which the alkylthio group may have is not particularly limited as long as it does not significantly inhibit the effect of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

The arylthio group for R ^{1 to} R ³ is usually 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Specific examples thereof include phenylthio group and tolylthio group. The substituent which the arylthio group may have is not particularly limited as long as it does not significantly inhibit the effect of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxy group, an alkoxy group, an aryloxy group and an alkyl And aryloxy groups, amino groups, aminoalkyl groups, sulfide groups and the like, and the molecular weight thereof is usually about 200 or less. In addition, hetero atoms such as oxygen, nitrogen, sulfur and phosphorus may be contained in this substituent.

Further, R ¹ and R ² , R ² and R ³ , and R ³ and R ¹ may be linked to each other to form a ring.

  Specific examples of the amine (1) include ammonia, methylamine, ethylamine, butylamine, octylamine, nonylamine, 1-aminodecane, primary amines such as aniline and phenethylamine, dimethylamine, diethylamine, dibutylamine and dipentyl Secondary amines such as amine, dihexylamine, diheptylamine, dicyclohexylamine, N-methylaniline etc., trimethylamine, triethylamine, tertiary amine such as tributylamine, tripentylamine, N, N-dimethylaniline etc., acetaldoxime etc. Diamines such as oximes, 1,3-propanediamine, N, N-dimethyl-1,6-hexanediamine, N-butylpyrrole, N-butyl-2,3-dihydropyrrole, N-butylpyrrolidine, 2,3 - 5-membered cyclic amines such as hydro-1H-indole, 4-aminomethylpiperidine, 4-dimethylaminopyridine, 1,2,3,4-tetrahydroquinoline, 4-amino-5,6-dihydro-2-methylpyrimidine, As a six-membered cyclic amine such as 2,3,5,6-tetramethylpyrazine, 3,6-dimethylpyridazine, etc., and a linear aliphatic hydrocarbon having two or more primary amino groups bound from an anion exchange resin. From the viewpoint of basicity, a polymer containing two or more, preferably 3 to 20, structural units derived from the nitrogen-containing compound represented by the formula (1) is preferable, and further, an ethanolamine, N , Linear amino alcohols such as N-dimethylethanolamine, 4-aminobutanol, 2-aminobutanol, 2-ethylmorpholine, N-methoxy Rubo sulfonyl morpholine, prolinol, 3-hydroxy-piperidine, 4-hydroxypiperidine, tetrahydrofurfuryl amines, cyclic amines, such as 3-amino-tetrahydrofuran and tetrahydropyran.

  Among them, an amine containing two or more nitrogen atoms is preferable from the viewpoint of suppressing the decomposition of polyalkylene ether glycol, and examples thereof include methylene diamine, ethylene diamine, butylene diamine, pyrazine and the like. In addition, a compound having a boiling point temperature of −40 to 120 ° C. at atmospheric pressure is preferable, since distillation may be performed in order to finally remove the nitrogen-containing compound from the polyalkylene ether glycol composition. Among them, ammonia, methylamine, ethylamine, butylamine, dimethylamine, diethylamine, trimethylamine, acetaldoxime, ethylenediamine and the like are preferable.

  Further, as the amide, an amide represented by the following formula (2) (hereinafter sometimes referred to as "amide (2)"), preferably carboxylic acid amide can be mentioned.

As the carboxylic acid amide, primary amide, secondary amide, tertiary amide can be used, and the number of N-substituted substituents is in the range of 0 to 2 N-alkyl substituted amide, N-alkenyl substituted amide, N-aryl A substituted amide or the like, that is, a carboxylic acid amide in which one or both of the substituents R ^a and R ^b are any of an alkyl group, an alkenyl group and an aryl group is used. The substituents R ^a and R ^b may contain hetero atoms, and the substituents R ^a and R ^b may be the same or different. On the other hand, examples of the substituent R ^c on the carbonyl side include a hydrogen atom, an alkyl group, an alkenyl group and an aryl group.
The substituents R ^{a to} R ^c may be linked to each other to form a ring. From the viewpoint of suppressing side reactions, decomposition and the like, an alkyl group is preferable as the substituent R ^c on the carbonyl side.

  Specific examples of the amide (2) include amides of chain skeleton such as acetamide, N-methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, and succinic acid amide, and aromatic amides such as benzamide Preferred are cyclic amides such as 2-pyrrolidone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, 2-piperidone, N-methyl piperidone and the like from the viewpoint of compound stability, and acetamide, N-methyl acetamide, 2 -Pyrrolidone and N-methyl pyrrolidone are more preferable from the viewpoint that the boiling point is not too high and the compound stability is also excellent. Among these, 2-pyrrolidone and N-methylpyrrolidone are particularly preferable.

  The nitrogen-containing compound contained in the polyalkylene ether glycol composition of the present invention has a molecular weight of usually 17 or more and 500 or less from the viewpoint of suppression of deposition on a catalyst used for purification of the polyalkylene ether glycol and removal by distillation. And more preferably 17 or more and 300 or less, and particularly preferably 17 or more and 200 or less. If the molecular weight is a nitrogen-containing compound having the above lower limit or more, volatilization in the process may be prevented. On the other hand, if the nitrogen-containing compound having the above upper limit or less is deposited on a catalyst used for purification of polyalkylene ether glycol. Is preferable because it can be suppressed by distillation and can be separated by distillation.

  Examples of amines that satisfy a suitable boiling point of the above-mentioned nitrogen-containing compound and that contain two or more nitrogen atoms that satisfy the above molecular weight include ethylenediamine and pyrazine.

  The polyalkylene ether glycol composition of the present invention may contain only one of these amines and amides as a nitrogen-containing compound, or may contain two or more of them, and both amines and amides may be contained. It may be included.

  The polyalkylene ether glycol composition of the present invention further comprises tetrohydrofuran, and the content of tetrahydrofuran is preferably at least 5 mass ppm, more preferably at least 10 mass ppm, particularly preferably at least 50 mass ppm, relative to the polyalkylene ether glycol. Usually, it is preferably 500 mass ppm or less, and more preferably 200 mass ppm or less. If the tetrahydrofuran content is more than the above upper limit, when performing vacuum distillation for purification of polyalkylene ether glycol etc., the degree of vacuum in the vacuum distillation column is deteriorated, or polyalkylene ether glycol is used as a raw material for urethane etc. If it does, it may become a volatile component and may deteriorate the work environment. On the other hand, excessive purification may be required to reduce the content of tetrohydrofuran below the upper limit.

  The polyalkylene ether glycol composition of the present invention has an acetal number of usually 0.01 mg-KOH / g or more, preferably 0.05 mg-KOH / g or more, particularly preferably 0.10 mg-KOH / g or more, usually 3.0 mg It is preferable that it is -KOH / g or less, further 1.0 mg-KOH / g or less, and particularly 0.3 mg-KOH / g or less. When the acetal number of the polyalkylene ether glycol composition is less than or equal to the above upper limit, a crosslinking reaction starting from an acetal when using a polyalkylene ether glycol as a raw material such as urethane can be suppressed, which is preferable. On the other hand, excessive purification may be required to make the acetal number less than the above lower limit.

  The nitrogen equivalent concentration, tetrohydrofuran content, and acetal value of the nitrogen-containing compound in the polyalkylene ether glycol composition of the present invention are measured by the methods described in the section of Examples described later.

The peroxide concentration of the polyalkylene ether glycol composition of the present invention is usually 0.01 μg-H ₂ O ₂ / g or more, preferably 0.02 μg-H ₂ O ₂ / g or more, more preferably 0.03 μg- H ₂ O ₂ / g or more. Meanwhile, the upper limit is usually _{3.0μg-H 2 O 2} / g or less, preferably _{2.0μg-H 2 O 2} / g, more preferably not more than _{1.5μg-H 2 O 2 / g} . If the peroxide concentration is too high, the acetal value and the carbonyl value become too high, which is not preferable, and the catalyst deterioration by oxidation and the formation of cyclic ethers by radicals tend to be promoted. On the other hand, excessive purification may be required to make the peroxide concentration be less than the above lower limit value.
Here, as the peroxide contained in the polyalkylene ether glycol composition of the present invention, the linear ether moiety of polyalkylene ether glycol is oxidized to have peroxy groups, and the cyclic ether moiety of tetrahydrofuran is oxidized to form peroxy 1 type, or 2 or more types, such as what has group, is mentioned, Usually, it originates in the chain-like ether part of polyalkylene ether glycol being oxidized, and is contained in a polyalkylene ether glycol composition.
The peroxide concentration in the polyalkylene ether glycol composition can be measured by a method of titrating iodine liberated by reaction with potassium iodide with sodium thiosulfate or the like.

In the polyalkylene ether glycol composition of the present invention, the concentration thereof is usually 10 mass ppm or more, particularly 50 parts by weight with respect to the polyalkylene ether glycol, by adding an antioxidant in order to suppress the above-mentioned problems caused by oxidation. It is preferable that the content is at least mass ppm, particularly at least 100 mass ppm. On the other hand, the upper limit of the antioxidant concentration with respect to the polyalkylene ether glycol is usually 1000 mass ppm or less, preferably 500 mass ppm or less, more preferably 300 mass ppm or less. If the antioxidant concentration is too high, it will lead to blockage due to solid precipitation in the process. On the other hand, when the antioxidant concentration is too low, the prevention of the above-mentioned oxidation reaction becomes insufficient, which is not preferable.
As the antioxidant, 2,6-di-tert-butyl-p-cresol (BHT) is preferable from the viewpoint of effect and stability.

  In such a polyalkylene ether glycol composition of the present invention, in the method for producing a polyalkylene ether glycol composition described below, preferably, a step of reducing acetal using a polyalkylene ether glycol composition containing a nitrogen-containing compound is used. Preferably, the acetal reduction step is a step of reducing the acetal contained in the polyalkylene ether glycol composition with a solid catalyst.

  The method for incorporating the nitrogen-containing compound into the polyalkylene ether glycol composition of the present invention is not particularly limited, and as described in the section of Examples described later, the above-mentioned nitrogen may be added to the produced polyalkylene ether glycol. The method of adding the contained compound so as to obtain the above-mentioned concentration in terms of nitrogen atom, and the preparation of polytetramethylene ether glycol containing nitrogen-containing compound using nitrogen-containing compound as raw material for producing polytetramethylene ether glycol Methods etc.

[Method for Producing Polyalkylene Ether Glycol Composition]
In the present invention, the method for producing the polyalkylene ether glycol is not particularly limited, but preferably, it is polytetra by ring-opening polymerization reaction of cyclic ether (may be a derivative of cyclic ether as described later) according to a conventional method. The method of manufacturing the diester body of methylene ether glycol and manufacturing polytetramethylene ether glycol by hydrolysis or transesterification of the diester body of this polytetramethylene ether glycol is mentioned.

<Cyclic ether>
In the present invention, the cyclic ether and derivatives thereof as raw materials for ring-opening polymerization reaction during production of polytetramethylene ether glycol are not particularly limited, but the number of carbon atoms constituting the cyclic ether is usually 2 to 10, preferably 3-7.
Specifically, tetrahydrofuran (THF), ethylene oxide, propylene oxide, oxetane, tetrahydropyran, oxepan, 1,4-dioxane and the like can be mentioned.
Further, derivatives of cyclic ethers in which part of the hydrogen atoms of the hydrocarbon group constituting the ring are substituted with an alkyl group or a halogen atom can also be used. Specifically, 3-methyltetrahydrofuran, 2-methyltetrahydrofuran and the like can be mentioned.

Although these cyclic ethers may be used 1 type or in mixture of 2 or more types, it is preferable to use by 1 type.
Among these, THF is preferable from the viewpoint of reactivity and the industrial demand for the obtained polyalkylene ether glycol.

  THF can be obtained by a conventionally known production method. For example, an acetoxylation reaction is carried out using raw materials butadiene, acetic acid and oxygen to obtain an intermediate diacetoxybutene, which is hydrogenated to hydrolyze the diacetoxybutene. Method to obtain by chemical dehydration; Method to obtain 1,4-butanediol obtained by hydrogenating maleic acid, succinic acid, maleic anhydride and / or fumaric acid as raw materials to obtain 1,4-butanediol; A method of cyclodehydration of 1,4-butanediol obtained by hydrogenating butynediol obtained by contacting with aqueous formaldehyde solution as cyclization dehydration of 1,4-butanediol obtained via oxidation of propylene; Method to obtain by dehydration; Method to obtain by cyclodehydration of 1,4-butanediol obtained by hydrogenating succinic acid obtained by fermentation method; Methods that may be cyclodehydration of 1,4-butanediol obtained by fermentation directly from biomass; and the like.

<Carboxylanhydride>
In the ring-opening polymerization reaction of cyclic ether, carboxylic anhydride may be used as an auxiliary agent (polymerization initiator). The carboxylic acid anhydride includes a carboxylic acid anhydride derived from an aliphatic or aromatic carboxylic acid having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Although it is preferable that the carboxylic acid used as the raw material of an anhydride is a monocarboxylic acid, you may use a polycarboxylic acid.

  Specific examples of the above carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, caprylic acid, pelargonic acid, maleic acid, aliphatic carboxylic acids such as succinic acid, etc .; benzoic acid, phthalic acid, naphthalene And aromatic carboxylic acids such as acids. Among these, it is preferable to use an anhydride derived from aliphatic carboxylic acid in view of price and availability, and acetic anhydride is preferably used in terms of reactivity and supply and demand of the obtained polyalkylene ether glycol.

  The amount of use of the carboxylic acid anhydride is not particularly limited, but usually 3 mol% or more, preferably 4 mol% or more, more preferably 5 mol% to the total of the raw material cyclic ether (may be a derivative). The upper limit is usually 30 mol% or less, preferably 28 mol% or less, more preferably 26 mol% or less, and still more preferably 25 mol% or less. When the amount of use of the carboxylic acid anhydride is too large, coloration derived from the carboxylic acid anhydride tends to occur in the ring-opening polymerization reaction or in the heating step after the ring-opening polymerization reaction, and the hue of the produced polyalkylene ether glycol diester May be worse. In addition, when the amount of use of the carboxylic acid anhydride is too small, a sufficient ring-opening polymerization reaction rate can not be obtained, and it may not be possible to produce the polyalkylene ether glycol diester with sufficient productivity.

<Polymerization catalyst>
A polymerization catalyst is usually used in the ring-opening polymerization reaction of cyclic ether.
The polymerization catalyst used here is not particularly limited as long as it is an acid catalyst capable of ring-opening polymerization of cyclic ether. The conventionally known methods are those using strong acid catalysts such as fluorosulphuric acid and are produced commercially. The polymerization catalyst is more preferably a solid acid catalyst having Lewis acidity.

As a solid acid catalyst, a solid acid catalyst consisting of a metal oxide is suitably used.
The metal is preferably a metal of Group 3, Group 4, Group 13, Group 14 or Group 14 of the periodic table (in the present invention, the periodic table refers to that according to IUPAC Inorganic Chemical Nomenclature, Revised Edition (1998)). The metal oxide which consists of a metal element to which it belongs, or the complex oxide containing these metal elements is used. Specifically, metal oxides such as yttrium oxide, titania, zirconia, alumina and silica; or complex oxides such as zirconia silica, hafnia silica, silica alumina, titania silica and titania zirconia are preferable. In addition, complex oxides further containing other metal elements may be used as these complex oxides.

As a method of preparing a solid acid catalyst used in the present invention, for example, a salt of one or more metals selected from metal elements belonging to Groups 3, 4, 13 or 14 of the periodic table or a salt thereof A method of forming a precipitate or gel as a solid acid catalyst precursor by adding an acid, an alkali, or water as necessary to a mixed solution containing an alkoxide may be mentioned. Precipitation method, sol-gel method, kneading method, impregnation method and the like can be mentioned.
In the present invention, a metal salt and / or a metal alkoxide is supported on a suitable carrier, and solid phase is obtained through the process of contacting a basic substance such as an alkali or an amine in a solid phase state (state substantially free of water). A method of obtaining an acid catalyst precursor is preferably used.

  The solid acid catalyst precursor thus obtained is subjected to filtration, washing and drying as necessary, and then under an inert gas atmosphere such as nitrogen and argon, or an oxidizing gas atmosphere such as air or diluted oxygen gas. The desired (composite) oxide can be obtained. The heating and firing temperature is usually 600 to 1150 ° C., preferably 700 to 1000 ° C. By baking in the said temperature range, the solid acid catalyst excellent in activity and stability can be obtained.

  The amount of polymerization catalyst used in the ring-opening polymerization reaction varies depending on whether the reaction mode is a fixed bed or a suspension bed, or whether it is a continuous reaction or a batch reaction. In general, the amount is usually 0.001 to 50% by mass, preferably 0.01 to 30% by mass, and particularly preferably 0.1 to 20% by mass, based on all the compounds in the reaction system.

<Ring-opening polymerization reaction>
A polyalkylene ether glycol diester can be obtained by conducting a ring-opening polymerization reaction using the above-mentioned cyclic ether and carboxylic acid anhydride and an acid catalyst as a ring-opening polymerization catalyst. The obtained polyalkylene ether glycol diester can be converted to a polyalkylene ether glycol by a known method such as hydrolysis or transesterification.
For example, when using THF as the cyclic ether, PTME is obtained. PTMG can be obtained by mixing the PTME with an aliphatic alcohol having 1 to 4 carbon atoms and performing transesterification by alcoholysis reaction in the presence of a transesterification catalyst.

  The reactor for conducting the ring-opening polymerization reaction is not particularly limited, but generally used reactors such as tank type and column type are used. The reaction system is also not particularly limited as long as it is a known method. As a specific example of the reaction system, a method (batch system) in which cyclic ether, carboxylic acid anhydride and polymerization catalyst are charged in a reactor and polymerization is carried out, and cyclic ether, carboxylic acid anhydride and polymerization catalyst are each constant in the reactor The method of continuously extracting the reaction liquid containing the target product, ie, the polyalkylene ether glycol diester, simultaneously with continuously supplying so that the amount is present (continuous system) can be mentioned. Among these, the continuous method is preferable because of excellent productivity.

  The ring-opening polymerization reaction temperature according to the present invention is not limited as long as it is a known range, but is usually 25 ° C. or more, preferably 30 ° C. or more, more preferably 33 ° C. or more, and the upper limit is usually 66 ° C. or less, preferably Is 60.degree. C. or less, more preferably 49.degree. C. or less. When the ring-opening polymerization reaction temperature exceeds the upper limit temperature, quality deterioration such as deterioration of coloring of the polyalkylene ether glycol diester may be caused. In addition, when the ring-opening polymerization reaction temperature is less than the lower limit temperature, not only the productivity is deteriorated due to the decrease in yield, but also unreacted raw materials (means unreacted cyclic ether used for raw materials and carboxylic acid anhydride). It tends to increase the cost of recovering the The ring-opening polymerization reaction temperature in the present invention means the liquid temperature in the reactor.

The ring-opening polymerization reaction pressure may be selected so that the reaction system can maintain the liquid phase, and is usually selected from the range of normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
The ring-opening polymerization reaction time is usually in the range of 0.1 to 20 hours, preferably 0.5 to 15 hours, from the viewpoint of the yield of the polyalkylene ether glycol diester and the economy. The reaction time mentioned here means, in the batch system, the time from the time when the reaction temperature is raised to the end of the reaction and the start of cooling, and in the continuous mode, the reaction time of the polymerization reaction solution in the reactor is It means the residence time.

  In the present invention, if necessary, a step of recovering unreacted starting material from the reaction liquid, purification of the obtained polyalkylene ether glycol diester, and hydrolysis step, purification of the polyalkylene ether glycol, and catalyst are carried out in the latter stage of the reactor. A regeneration step or the like may be added.

  In the case of the batch reaction system, after completion of the reaction, the catalyst and the reaction solution are first filtered and fractionated, and the unreacted starting material is distilled off from the reaction solution, whereby only the polymer can be easily obtained. Furthermore, after the reaction, the catalyst can be easily recovered in activity by thoroughly washing the deposited organic matter.

  In the production method of the present invention, when a separation / recovery step of unreacted raw materials is added, it is not particularly limited as long as it is a known method such as using a gas-liquid separator or a gas-liquid contactor. It is preferable that the process of supplying the reaction liquid containing glycol diester and separating and collecting an unreacted raw material is included. In addition, one or more separation and recovery steps of these unreacted raw materials may be combined. The gas-liquid contact device means a device used in the step of bringing an inert gas into contact with a reaction liquid containing polytetramethylene ether glycol diester.

<Hydrolysis or transesterification reaction>
In order to convert a polyalkylene ether glycol diester into a polyalkylene ether glycol, polytetramethylene ether glycol diester may be hydrolyzed in the presence of a catalyst or transesterified with a lower alcohol.

  The catalyst is not particularly limited as long as it is a known one used for hydrolysis reaction and transesterification reaction, but usually, alkali metal alkoxides such as lithium, sodium, potassium, cesium, rubidium and the like are used, among which sodium And potassium alkoxides are preferably used. Specifically, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide and the like can be mentioned. Sodium methoxide is more preferred because it is versatile and inexpensive.

  As the lower alcohol used for the transesterification of polytetramethylene ether glycol diester, aliphatic alcohols having 1 to 4 carbon atoms such as methanol and ethanol are used, but from the viewpoint of the reaction rate of transesterification, methanol is preferred. Used. The lower alcohol is usually used in an amount of about 10 to 500% by mass with respect to polytetramethylene ether glycol diester.

  The hydrolysis reaction or transesterification reaction can usually be carried out under normal pressure or under pressure, and the pressure is usually 0.1 to 2.0 MPa, preferably 1.0 to 1.5 MPa. Moreover, the reaction temperature in a hydrolysis reaction or transesterification is normally performed in 60-180 degreeC.

Purification of Crude Polytetramethylene Ether Glycol
The method for purifying the crude polyalkylene ether glycol obtained by hydrolysis or transesterification of the polyalkylene ether glycol diester is not particularly limited. However, an oligomer having an organic impurity or dimer to pentamer as a center is obtained by distillation. The method of removal, the method of removing a water-soluble substance by extraction, the method of hydrogenating to reduce the acetal value, the carbonyl value or the coloring, and the like can be mentioned. These purifications may be used alone or in combination of two or more. In the present invention, it is preferable to include a method of reducing the acetal number, the carbonyl number and the coloration by decomposing the acetal by hydrogenation.

  As a hydrogenation catalyst used for hydrogenation of crude polytetramethylene ether glycol, metal elements belonging to Groups 8 to 11 of the periodic table, that is, iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), Uniform containing at least one of rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag) and gold (Au) A system catalyst or a solid catalyst in which these metal elements are supported on a carrier can be mentioned. Among these, metal elements belonging to Group 10 of the periodic table are preferable, and among them, a palladium solid catalyst is most preferable in terms of catalyst cost and catalyst activity.

  The form of the metal element belonging to Group 8 to 11 of the periodic table in the solid catalyst may be a simple metal, an oxide, a hydroxide, other various salts, and the like. If the ratio of oxides to simple metals is high, it is also possible to carry out a process of converting them into simple metals by, for example, performing reduction activation treatment in advance with hydrogen gas before starting the reaction. However, it is safe to start the reaction as it is. That is, since hydrogen gas is introduced into the hydrogenation reaction system, these oxides and the like are reduced during the reaction to become an active metal element.

  On the other hand, as the carrier, it is preferable to use one or two or more of silica, alumina, titania, zirconia, activated carbon, graphite, diatomaceous earth and the like. Among them, silica and / or diatomaceous earth is preferable, and silica is particularly preferable.

  Metal element component content belonging to periodic table groups 8 to 11 in solid catalyst (herein, metal element component content belonging to periodic table groups 8 to 11 in solid catalyst means periodic table groups 8 to 11 When the metal element belonging to is in the form of a metal oxide etc., its content as metal oxide etc.) is usually at least 0.1 mass%, preferably at least 0.5 mass%, particularly preferably Is 1% by mass or more, and the upper limit is usually 80% by mass or less, preferably 20% by mass or less, and particularly preferably 10% by mass or less. If the content of the metal element component is less than the above range and the carrier content is high, the amount of the metal element as the catalytically active component is insufficient, so that high hydrogenation efficiency can not be obtained. Even if the amount is high and the carrier content is low, high hydrogenation efficiency can not be obtained due to the decrease in catalyst strength.

The solid catalyst in the present invention may contain other metal elements as long as it contains a metal element belonging to Groups 8 to 11 of the periodic table. Other metal elements that may be contained include, for example, chromium, manganese, zinc, magnesium, sodium, rhenium, calcium and the like. These metal elements may also be contained in the form of metal elements themselves, oxides, hydroxides, and various other salts. When the other metal component is contained, the content thereof in the solid catalyst is usually 0.1% by mass or more, preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and the upper limit thereof is Usually, the content is 20% by mass or less, preferably 15% by mass or less, particularly preferably 10% by mass or less.
Although the catalytic activity can be improved by combined use of such other metal components, a sufficient combined effect can not be obtained if the content is too small, and if too large, the periodic table eighth will be relatively The content of the Group 11 metal element and the support decreases, which may impair the original hydrogenation catalyst activity and selectivity of the solid catalyst according to the present invention, resulting in an increase in the amount of high-boiling by-products generated. There is also fear.

  The shape and size of the solid catalyst are not particularly limited, and may be powder, granules, granules, or molded articles such as pellets. Also, the size of the solid catalyst is optional, but for example, in the case of a solid catalyst shaped into a pellet, it is preferable that the diameter is 1 to 20 mm and the thickness is 1 to 20 mm.

  Such a solid catalyst may be produced by immersing the support in an aqueous solution of a metal salt of Group 8-11 of the periodic table to support the metal salt, calcining it, and if necessary forming it, etc. it can.

  The reaction temperature for carrying out the hydrogenation in the present invention is usually 0 ° C. or more, preferably 50 ° C. or more, particularly preferably 100 ° C. or more. The upper limit is usually 200 ° C. or less, preferably 180 ° C. or less, particularly preferably 150 ° C. or less. If this temperature is too high, the amount of cyclic ether by-product increases and catalyst deterioration is promoted. Furthermore, the amount of high-boiling by-products will increase. If the reaction temperature is too low, the reaction hardly proceeds and the intended purification effect can not be obtained.

  The hydrogen gas pressure in the hydrogenation is usually at least 0.1 MPa, preferably at least 0.5 MPa, particularly preferably at least 1 MPa in gauge pressure. The upper limit is usually 100 MPa or less, preferably 10 MPa or less, and particularly preferably 6 MPa or less. If this pressure is too low, the reaction rate is slow and productivity is reduced. If the pressure is too high, the pressure resistance load of the reactor and the compressor load will increase, and the construction cost will increase significantly.

  In addition, the residence time of the reaction solution on the basis of an empty column during the hydrogenation reaction is usually 5 minutes or more, preferably 10 minutes or more, and particularly preferably 30 minutes or more. Also, it is usually 20 hours or less, preferably 8 hours or less, particularly preferably 5 hours or less. If this residence time is too short, the reaction hardly proceeds. On the other hand, if the reactor is too long, for example, in the case of a packed bed type hydrogenation reactor, the catalyst packed bed becomes large, and the cost of the reactor increases and the amount of catalyst increases the economic efficiency significantly.

  The reaction can be carried out using all fixed bed, trickle bed, multi-tubular, etc. various solid catalyst general packed bed type hydrogenation reactors, but preferably the fixed bed reactor and the trickle bed reactor It is either. This reactor may use only one machine, and it is possible to use a plurality of machines in multiple stages.

  In the hydrogenation of crude polytetramethylene ether glycol, crude polytetramethylene ether glycol may be diluted with a solvent inert to the reaction and subjected to reaction in order to facilitate contact with a solid catalyst. In this case, one or two or more of methanol, toluene and the like can be used as a dilution solvent, and the crude polytetramethylene ether glycol is diluted to about 5 to 95% by mass in solid content concentration and used for the reaction. Is preferable from the viewpoint of miscibility with hydrogen.

  The polyalkylene ether glycol composition of this invention can be obtained by passing through the acetal reduction process by hydrogenation which used such a solid catalyst. The resulting polyalkylene ether glycol composition has a low acetal number, and problems such as coloring are reduced, and can be suitably used for various applications.

  The polyalkylene ether glycol composition of the present invention is further subjected to a purification treatment such as cation exchange resin treatment or distillation to reduce the content of nitrogen-containing compound after passing through the above-described acetal reduction step by hydrogenation. Then, it may be used for various applications described later.

[Application of Polyalkylene Ether Glycol Composition]
The polyalkylene ether glycol composition of the present invention can be used as a raw material for producing elastic fibers, polyurethanes, synthetic leathers, thermoplastic polyester elastomers, thermoplastic elastomers such as thermoplastic polyurethane elastomers, coating materials and the like.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Molecular weight measurement method]
The number average molecular weight (Mn) of PTMG was analyzed by gel permeation chromatography (GPC). For calibration of GPC, POLYTE TRAHYDROFURAN calibration kit manufactured by POLYMER LABORATORIES, UK was used.

[Method for measuring acetal number]
The acetal concentration in PTMG was determined from neutralization titration of 0.1 N methanolic potassium hydroxide solution by adding 10 mL of 1 N hydrochloric acid hydroxylamine hydrochloride to 10 g of sample and reacting at 60 ° C. for 2 hours for liberated hydrochloric acid . However, in Comparative Example 2 and Example 3 and Example 4, since the contained nitrogen-containing compound reacts with the titration solution, it is determined by ¹ H NMR from the ratio of methylene hydrogen next to PTMG hydroxyl group end and methine hydrogen of acetal structure. The The acetal number was determined from the acetal concentration measured, and all the units were standardized to mg-KOH / g on a titration basis.

[Nitrogen analysis method]
The nitrogen-containing compound content in the sample was determined by burning the sample in an atmosphere of argon and oxygen, and burning the generated combustion gas using a trace nitrogen meter (TN-10 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using the reduced pressure chemiluminescence method. And determined by analysis. However, in Example 4, the concentration in terms of nitrogen atom was calculated from the amount of amine added.

[THF analysis method]
The THF concentration contained in PTMG was calculated by gas chromatography (apparatus: manufactured by Shimadzu Corporation, model number GC-2014, column DB-1) and calculated by the internal standard method.

[Open ring polymerization catalyst]
As a ring-opening polymerization reaction catalyst for THF, a 27.2% aqueous solution of zirconia nitrate is impregnated with CARiACT Q 15 (registered trademark) (silica carrier manufactured by Fuji Silysia Chemical Ltd.) and then dried and then treated with bicarbonate After neutralization and washing with an aqueous ammonium solution, those dried and calcined at 900 ° C. were used.

Preparation Example 1: Preparation of acetal-containing PTMG
While bubbling air at a flow rate of 50 mL / min into 500 g of tetrahydrofuran manufactured by Mitsubishi Chemical Co., Ltd., which does not contain an antioxidant, air contact treatment was carried out at room temperature and normal pressure for 24 hours. Air-contacted tetrahydrofuran is charged in a 500 mL flask reactor made of glass, 405 g, 49.5 g of acetic anhydride made by Daicel Corporation, 18 g of ring-opening polymerization catalyst, and reacted for 6 hours at a reaction temperature of 40 ° C. under a nitrogen atmosphere. I did. 100 g of a polymerization reaction solution obtained by filtering and separating the catalyst from this reaction solution is put into a glass round bottom flask equipped with a stirrer, and while bubbling nitrogen at a flow rate of 500 mL / min, bath temperature under normal pressure The unreacted raw material was distilled off by heating at 170 ° C. for 2 hours to obtain about 120 g of PTME.

Next, 100 g of the obtained PTME, 200 g of methanol manufactured by Kanto Chemical Co., Ltd., and 0.34 g of a 24% sodium methoxide methanol solution manufactured by Tokyo Chemical Industry Co., Ltd. were placed in a glass separable flask. The temperature of the oil bath was raised to 90 ° C. while stirring at 250 rpm, and 100 g of methanol was withdrawn after total reflux for 1 hour. When the internal temperature reached 60 ° C. or less, 100 g of methanol was added, the temperature of the oil bath was raised to reflux for 1 hour, and 100 g of methanol was extracted. To the solution remaining in the flask was added 20 g of sulfonic acid-based strongly acidic cation exchange resin (diaion PK216) manufactured by Mitsubishi Chemical Co., Ltd. to remove alkali. After removing the resin by pressure filtration, the solvent was distilled off at 120 ° C. under a reduced pressure of 0.2 MPa or less to obtain PTMG-1.
The number average molecular weight of obtained PTMG-1 was 2053, and the acetal number was 1.36 mg-KOH / g.

Preparation Example 2 Preparation of Nitrogen-Containing PTMG
500 g of tetrahydrofuran made by Mitsubishi Chemical Co., Ltd. 500 g of styrenic polyamine type anion exchange resin (Diaion WA20) made by Mitsubishi Chemical Co., Ltd. and heated at 70 ° C. for about 24 hours using a 1 L stainless steel autoclave, then ion exchange The resin was separated by filtration to prepare tetrahydrofuran containing a nitrogen-containing compound of anion exchange resin eluate. At this time, the recovered tetrahydrofuran contained about 15 ppm of a nitrogen-containing compound in terms of nitrogen atom concentration. In Preparation Example 1, PTME is similarly produced by a ring-opening polymerization reaction except that this nitrogen-containing tetrahydrofuran is used as tetrohydrofuran, and a transesterification reaction of PTME is similarly carried out to obtain PTMG-2 The The number average molecular weight of the obtained PTMG-2 was 1802, and the nitrogen-containing compound was contained at 4 mass ppm in terms of nitrogen atom.

Preparation Example 3 Preparation of High Concentration Nitrogen-Containing PTMG
Add 500 g of styrenic polyamine type anion exchange resin (Diaion WA20) made by Mitsubishi Chemical Co., Ltd. to 500 g of tetrahydrofuran made by Mitsubishi Chemical Co., Ltd. and heat it at 70 ° C for about 72 hours using a 1 L stainless steel autoclave and then ion exchange The resin was separated by filtration to prepare tetrahydrofuran containing a nitrogen-containing compound of anion exchange resin eluate. At this time, the recovered tetrahydrofuran contained about 200 ppm of a nitrogen-containing compound in terms of nitrogen atom concentration.
300 g of this nitrogen-containing tetrahydrofuran and 100 g of PTMG (Mn = 1800) manufactured by Mitsubishi Chemical Corporation are placed in a glass round bottom flask equipped with a stirrer, and nitrogen is bubbled at a flow rate of 500 mL / min under normal pressure. The unreacted raw materials were distilled off by heating at a bath temperature of 170 ° C. for 2 hours to obtain about 100 g of PTMG-3.
The number average molecular weight of the obtained PTMG-3 was 1800, and the nitrogen-containing compound was contained at 550 mass ppm in nitrogen atom equivalent concentration.

Comparative Example 1
15.6 g of PTMG-1 obtained in Preparation Example 1 and 9.4 g of PTMG (Mn = 1800) manufactured by Mitsubishi Chemical Corporation (hereinafter sometimes referred to as “product PTMG”) were mixed. The number average molecular weight of PTMG obtained by mixing was 1950, and the nitrogen-containing compound content in nitrogen atom equivalent concentration was 0 mass ppm. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.42 mg-KOH / g.
This mixed solution is transferred to a 100 mL stainless steel autoclave, and 1 g of a catalyst in which 1.0% by mass of Pd is supported on a cylindrical activated carbon with a diameter of 3 mm and a length of 3 mm is added, and hydrogen gas pressure 0.7 MPaG at 130 ° C. A 6 hour hydrocracking reaction was performed. The acetal value in the mixture after reaction was 0.23 mg KOH / g, and 734 ppm by mass of tetrahydrofuran was contained. At this time, the hydrogenolysis rate of acetal is 45.2%.

Comparative Example 2
15.6 g of PTMG-1 obtained in Preparation Example 1, 7.1 g of product PTMG, and 2.3 g of PTMG-3 obtained in Preparation Example 3 were mixed. The number average molecular weight of PTMG obtained by mixing was 1955, and the nitrogen-containing compound content was 50 mass ppm in terms of nitrogen atom concentration. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.43 mg-KOH / g.
When the hydrogenolysis reaction was implemented about this liquid mixture like comparative example 1, the acetal number in mixed solution after reaction was 0.43 mg-KOH / g, and 1166 mass ppm of tetrahydrofuran were contained. At this time, the hydrogenolysis rate of acetal is 0.0%.

Example 1
15.6 g of PTMG-1 obtained in Preparation Example 1, 8.8 g of a product PTMG, and 0.6 g of PTMG-2 obtained in Preparation Example 2 were mixed. The number average molecular weight of PTMG obtained by mixing was 1950, and the nitrogen-containing compound content was 0.1 mass ppm in terms of nitrogen atom concentration. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.41 mg-KOH / g.
When the hydrogenolysis reaction was implemented similarly to the comparative example 1 about this liquid mixture, the acetal value in the liquid mixture after reaction was 0.26 mg-KOH / g, and 492 mass ppm of tetrahydrofuran were contained. At this time, the hydrogenolysis rate of acetal is 36.6%.

Example 2
15.6 g of PTMG-1 obtained in Preparation Example 1, 3.2 g of a product PTMG, and 6.2 g of PTMG-2 obtained in Preparation Example 2 were mixed. The number average molecular weight of PTMG obtained by mixing was 1955, and the nitrogen-containing compound content was 1 mass ppm in terms of nitrogen atom concentration. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.42 mg-KOH / g.
When the hydrogenolysis reaction was implemented about this liquid mixture like comparative example 1, the acetal number in the liquid mixture after reaction was 0.24 mg-KOH / g, and 209 mass ppm of tetrahydrofuran were contained. At this time, the hydrogenolysis rate of acetal is 42.9%.

[Example 3]
15.6 g of PTMG-1 obtained in Preparation Example 1, 8.3 of product PTMG, and 1.1 g of PTMG-3 obtained in Preparation Example 3 were mixed. The number average molecular weight of PTMG obtained by mixing was 1950, and the nitrogen-containing compound content was 10 ppm by mass in terms of nitrogen atom. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.43 mg-KOH / g.
When the hydrogenolysis reaction was implemented about this liquid mixture like comparative example 1, the acetal number in mixed solution after reaction was 0.16-KOH / g, and 280 mass ppm of tetrahydrofuran were contained. At this time, the hydrogenolysis rate of acetal is 62.8%.

Example 4
15.6 g of PTMG-1 obtained in Preparation Example 1, 9.4 g of a product PTMG, and 0.015 g of diethylamine manufactured by Kanto Chemical Co., Ltd. were mixed. The number average molecular weight of PTMG obtained by mixing was 1950, and the nitrogen-containing compound content was 10 ppm by mass in terms of nitrogen atom. Furthermore, 25 g of toluene manufactured by Kanto Chemical Co., Ltd. was mixed to prepare a mixed solution. The acetal number of the mixed solution was 0.43 mg-KOH / g.
When the hydrogenolysis reaction was implemented similarly to the comparative example 1 about this liquid mixture, the acetal value in the mixed solution after reaction was 0.18 mg-KOH / g, and 132 mass ppm of tetrahydrofuran were contained. At this time, the hydrogenolysis rate of acetal is 58.1%.

  The results of Comparative Examples 1 and 2 and Examples 1 to 4 are summarized in Table 1 below. In Table 1, the nitrogen atom equivalent concentration of the nitrogen-containing compound is described as "N concentration".

  From Table 1, when the nitrogen-containing compound content of the mixed PTMG is in the range of 0.1 to 40 mass ppm in terms of nitrogen atom conversion, the acetal is excellent in the hydrocracking efficiency and the thermal decomposition during the hydrocracking reaction It is understood that the stability is also excellent, and the amount of decomposition product tetrohydrofuran is small.

Claims (16)

A polyalkylene ether glycol composition comprising a nitrogen containing compound, wherein
The polyalkylene ether glycol composition whose content of a nitrogen-containing compound is 0.1 mass ppm or more and 40 mass ppm or less as nitrogen atom conversion density | concentration with respect to polyalkylene ether glycol.   The polyalkylene ether glycol composition according to claim 1, wherein the nitrogen-containing compound is at least one of an amine and an amide.   The polyalkylene ether glycol composition according to claim 1 or 2, wherein the boiling point of the nitrogen-containing compound is -40 ° C or more and 120 ° C or less.   The polyalkylene ether glycol composition according to any one of claims 1 to 3, wherein the nitrogen-containing compound is an amine containing two or more nitrogen atoms.   The polyalkylene ether glycol composition according to any one of claims 1 to 4, wherein the nitrogen-containing compound is an anion exchange resin eluate.   The polyalkylene ether glycol composition according to any one of claims 1 to 5, wherein the molecular weight of the nitrogen-containing compound is 17 or more and 500 or less.   The composition according to any one of claims 1 to 6, wherein the polyalkylene ether glycol composition further comprises tetrohydrofuran, and the content of the tetrahydrofuran is 5 to 200 ppm by mass with respect to the polyalkylene ether glycol. The polyalkylene glycol composition as described in-.   The polyalkylene ether glycol composition according to any one of claims 1 to 7, which has an acetal number of 0.01 mg-KOH / g or more and 3.0 mg-KOH / g or less. Poly according to any one of claims 1 to 8 peroxide concentration is less _{0.01μg-H 2 O 2} / g or more _{3.0μg-H 2 O 2} / g with respect to polyalkylene ether glycol Alkylene ether glycol composition.   The polyalkylene ether glycol composition according to any one of claims 1 to 9, wherein the antioxidant concentration is 10 mass ppm or more and 1000 mass ppm or less with respect to the polyalkylene ether glycol. A method of producing the polyalkylene ether glycol composition according to any one of claims 1 to 10, wherein
A method for producing a polyalkylene ether glycol composition, comprising a purification step of reducing an acetal contained in the polyalkylene ether glycol composition.   The method for producing a polyalkylene ether glycol composition according to claim 11, wherein the acetal contained in the polyalkylene ether glycol composition is reduced by a solid catalyst in the purification step.   An elastic stretchable fiber using the polyalkylene ether glycol composition according to any one of claims 1 to 10.   A polyurethane using the polyalkylene ether glycol composition according to any one of claims 1 to 10.   A synthetic leather using the polyalkylene ether glycol composition according to any one of claims 1 to 10.   A thermoplastic elastomer using the polyalkylene ether glycol composition according to any one of claims 1 to 10.