JP2008007731A - Method for manufacturing polyoxyalkylene polyol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing efficiently a polyoxyalkylene polyol by an addition polymerization of an alkylene oxide in the presence of an acidic catalyst to the polyoxyalkylene polyol obtained by an addition polymerization of an alkylene oxide in the presence of an alkali metal catalyst. <P>SOLUTION: The method comprises a step of an addition polymerization of (c) an alkylene oxide to (b) an active hydrogen-containing compound in the presence of (a) an alkali metal catalyst to thereby give (d) the first crude polyoxyalkylene polyol, then a step of treatments in order of [1] addition of water to the above product (d) and removal of a water phase after the separation by using a liquid/liquid separating apparatus and of [2] two-stage neutralization with a weak acid and a strong acid and then of the dewatering to give (P) the polyoxyalkylene polyol composition consisting of (e) a neutralized salt, (g) a weak acid and a polyoxyalkylene polyol, and then a step of addition polymerization of (P) the above composition with (c) an alkylene oxide in the presence of (j) an acidic catalyst added. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polyoxyalkylene polyol composition and a polyoxyalkylene polyol composition.

  Usually, a polyoxyalkylene polyol is obtained by addition polymerization of an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali metal catalyst such as potassium hydroxide.

  On the other hand, addition polymerization of alkylene oxide proceeds also with an acidic catalyst such as a double metal cyanide (DMC) catalyst, a boron compound, or an aluminum compound. The addition polymerization of alkylene oxide using these acidic catalysts may use a polymer polyoxyalkylene polyol obtained with an alkali metal catalyst as a starting material.

  It is known that acidic catalysts are easily inactivated by alkali metal catalysts. Therefore, in order to carry out addition polymerization of alkylene oxide in the presence of an acidic catalyst to a crude polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide in the presence of an alkali metal catalyst, it is usually necessary to divide the reaction vessel into two. It becomes. That is, first, a first crude polyoxyalkylene polyol obtained by addition polymerization of an alkylene oxide with an alkali metal catalyst in a first reaction vessel is purified by a known method. In this refining stage, processing agent residue and waste water are generated as waste. This polyol is charged into a second reaction vessel, and an alkylene oxide addition polymerization is performed using an acidic catalyst. Further, when two reaction vessels are not used, it is necessary to completely wash the reaction vessel between batches and remove the pre-batch residue containing the remaining alkali metal catalyst. This cleaning requires a large amount of cleaning water and solvent. Therefore, in either case, the production efficiency is greatly reduced and a large amount of waste is discharged.

As a prior art, in Patent Document 1, an alkali metal catalyst derived from a previous batch is neutralized with an inducer containing a soluble acid such as dodecylbenzenesulfonic acid (DDBSA), and then addition polymerization with a DMC catalyst which is an acidic catalyst. A method of continuously performing is disclosed. However, the alkali metal catalyst that can be neutralized with acid in this manner is a small amount remaining in the crude polyoxyalkylene polyol derived from the previous batch remaining in the reaction kettle. Also, the amount of alkali metal catalyst usually used for addition polymerization of alkylene oxide (0.1 to 1.0% by weight of potassium hydroxide with respect to crude polyoxyalkylene polyol) is neutralized with a soluble acid such as DDBSA. Then, in some applications (for example, the production of flexible polyurethane foam), the disadvantage that DDBSA salt acts as an activator and adversely affects the foaming behavior is known.
JP 2005-163022 A

  In addition, a method of adding an acidic compound directly to a crude polyoxyalkylene polyol to neutralize an alkali metal catalyst is known, but after adding an acid, removal of residual alkali by a known means such as filtration with an adsorbent is performed. In the polyoxyalkylene polyol composition containing a neutralized salt obtained without implementation, the neutralization reaction of the alkali metal catalyst does not proceed completely even if it is acidic by pH measurement. Therefore, the reaction does not proceed even if an addition polymerization of alkylene oxide is attempted in the presence of an acidic catalyst in the polyol composition.

  In the present invention, polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide in the presence of an alkali metal catalyst is used as a starting material, and further, alkylene oxide is addition-polymerized in the presence of an acidic catalyst to make polyoxyalkylene polyol efficient. The object is to find a method for manufacturing the target.

As a result of intensive studies, the present inventors have reached the inventions shown in (I) to (IV) below.
That is, the present invention
(I) A first crude polyoxyalkylene polyol (d) obtained by addition polymerization of an alkylene oxide (c) to an active hydrogen-containing compound (b) in the presence of an alkali metal catalyst (a) is represented by the following [1] [2 ] A process for producing a polyoxyalkylene polyol composition (P) comprising a neutralized salt (e), a weak acid (g), and a polyoxyalkylene polyol, wherein the polyoxyalkylene polyol composition (P) is treated in this order.
[1] Water is added to the first crude polyoxyalkylene polyol (d), and after liquid separation using a liquid / liquid separator, the aqueous phase is removed to obtain the second crude polyoxyalkylene polyol (f).
[2] The second crude polyoxyalkylene polyol (f) is neutralized in two stages with a weak acid (g) and then with a strong acid (h), and then dehydrated to obtain (P).
(II) A neutralized salt (e), a weak acid, which is obtained by adding an acidic catalyst (j) to the polyoxyalkylene polyol composition (P) obtained by the production method described in (I) and subjecting the alkylene oxide (c) to addition polymerization. A process for producing a polyoxyalkylene polyol composition (Q) comprising (g) and a polyoxyalkylene polyol.
(III) A polyol composition comprising a weak acid (g) and a polyoxyalkylene polyol, wherein the neutralized salt (e) in the polyoxyalkylene polyol composition (Q) obtained by the production method described in (II) is removed by filtration. The manufacturing method of (R).
(IV) A polyacid comprising a weak acid (g) obtained by the production method described in (III) and having a residual alkali metal catalyst (a) and a neutralized salt (e) content of 1 ppm or less and a polyoxyalkylene polyol. Oxyalkylene polyol composition (R).
About.

  The production method of the present invention does not require purification of the first crude polyoxyalkylene polyol as compared with the conventional one, and uses two reaction vessels or performs complete washing between batches. Is also unnecessary. Therefore, the production efficiency is improved, and the desired polyoxyalkylene polyol can be obtained in a short time, and the generation of waste water, waste solvent, treatment agent residue, etc. is reduced as purification and washing are not required.

  In the present invention, as the alkali metal catalyst (a), alkali metal hydroxide (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholate (potassium methylate, sodium methylate, etc.), alkali metal simple substance ( Metal potassium, metal sodium, etc.), and mixtures of two or more of these. Of these, alkali metal hydroxides and alkali metal alcoholates are preferred.

  The active hydrogen-containing compound (b) is not limited as long as it generates a cyclic ether ring-opening adduct by reaction with the alkylene oxide (c). For example, a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound A compound, a thiol group-containing compound, a phosphate compound; a compound having two or more active hydrogen-containing groups in the molecule; and a mixture of two or more thereof. Further, those obtained by adding the above-mentioned alkylene oxide (c) to these active hydrogen-containing compounds (b) can also be used as starting materials for addition of alkylene oxide as long as active hydrogen is present.

Examples of the hydroxyl group-containing compound include water, monovalent alcohol, 2 to 8 valent polyhydric alcohol, phenols, and 2 to 8 valent polyhydric phenols.
Specifically, monohydric alcohols such as methanol, ethanol, butanol, octanol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentane Dihydric alcohols such as diol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane Trivalent alcohols such as glycerin and trimethylolpropane; 4-8 valents such as pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose Alcohols; phenols such as phenol and cresol; polyhydric phenols such as pyrogallol, catechol, and hydroquinone; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; polybutadiene polyols; castor oil-based polyols; ) Polymers, polyfunctional (2-100) polyols such as polyvinyl alcohol, and the like, and those having 1 to 20 carbon atoms are preferred.
Examples of the polybutadiene polyol include those having a 1,2-vinyl structure, those having a 1,2-vinyl structure and a 1,4-trans structure, and those having a 1,4-trans structure. The ratio of the 1,2-vinyl structure and the 1,4-trans structure can be changed in various ways, and for example, the molar ratio is 100: 0 to 0: 100. The polybutadiene glycol (4) includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.), and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%).
Castor oil-based polyols include castor oil and modified castor oil (castor oil modified with a polyhydric alcohol such as trimethylolpropane and pentaerythritol).

Examples of amino group-containing compounds include mono- or polyamines, and amino alcohols.
Specific examples of mono- or polyamines include monoamines such as ammonia, alkylamines (such as butylamine), and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine; piperazine, N-amino Ethyl piperazine and other heterocyclic polyamines described in JP-B No. 55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine Aromatic polyamines such as diphenyl ether diamine and polyphenylmethane polyamine; polyamide polyamines [for example, dicarboxylic acids (dimer acids etc.) and excess (acid 1 Low molecular weight polyamide polyamine obtained by condensation with 2 or more moles of polyamines (the above alkylene diamine, polyalkylene polyamine, etc.); polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.)] Cyanoethylated polyamines [for example, cyanoethylated polyamines obtained by addition reaction of acrylonitrile and polyamines (the above alkylenediamine, polyalkylenepolyamine, etc.), such as biscyanoethyldiethylenetriamine, etc .; hydrazines (hydrazine, monoalkylhydrazine, etc.), dihydrazides (Succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.), guanidines (butyl) Guanidine, 1-cyanoguanidine, etc.); and dicyandiamide; and mixtures of two or more thereof, with preferably from 1 to 20 carbon atoms.
Amino alcohols include alkanolamines such as mono-, di- and tri-alkanolamines (monoethanolamine, monoisopropanolamine, monobutanolamine, triethanolamine, tripropanolamine, etc.); To C4) Substituents [N, N-dialkylmonoalkanolamine (N, N-dimethylethanolamine, N, N-diethylethanolamine etc.), N-alkyldialkanolamine (N-methyldiethanolamine, N-butyldiethanolamine etc.) )]; And these quaternized nitrogen atoms by quaternizing agents such as dimethyl sulfate or benzyl chloride, and those having 1 to 20 carbon atoms are preferred.

Examples of the carboxyl group-containing compound include carboxylic acids having 1 to 20 carbon atoms; aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatics such as succinic acid and adipic acid Polycarboxylic acid; aromatic polycarboxylic acid such as phthalic acid, terephthalic acid, trimellitic acid; polycarboxylic acid polymer (functional number 2 to 100) such as (co) polymer of acrylic acid.
Examples of the polythiol compound of the thiol group-containing compound include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 3-methylpentanedithiol, and the like.
Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  Among these active hydrogen-containing compounds (b), preferred are hydroxyl group-containing compounds, and more preferred are polyhydric alcohols.

The alkylene oxide (c) to be subjected to addition polymerization in (b) is preferably one having 1 to 10 carbon atoms. Specific examples include ethylene oxide, propylene oxide, 1,2-, 1,3-, 1,4- , And 2,3-butylene oxide, and styrene oxide. Of these, preferred are propylene oxide and / or ethylene oxide, and more preferred is propylene oxide.
The number of moles of alkylene oxide (c) added to the active hydrogen-containing compound (b) is preferably 1 to 300 moles, more preferably 10 to 250 moles, particularly preferably 20 to 160 moles per mole of active hydrogen. is there.
Examples of the method for adding (c) include, but are not limited to, single addition, random addition when two or more kinds of (c) are used, and block addition.

The amount of the alkali metal catalyst (a) used is preferably 0.1 to 1.0% by weight, more preferably 0.11 to 0.5%, based on the obtained first crude polyoxyalkylene polyol (d). % By weight, more preferably 0.12 to 0.3% by weight. If it exceeds 0.1% by weight, the reaction time is short and efficient, and if it is 1.0% by weight or less, the addition polymerization reaction can be easily controlled, and the production of by-products such as double bond-containing compounds is small.
The addition reaction may be carried out by a usual method, and in the case of adding any of the above alkylene oxides (c), the temperature is preferably 80 to 160 ° C., the pressure is preferably 0 to 0.5 MPa, and the reaction time is preferably Can be carried out in 3 to 10 hours.
The first crude polyoxyalkylene polyol (d) thus obtained preferably contains 0.1 to 1.0% by weight of the alkali metal catalyst (a) with respect to (d).

The first crude polyoxyalkylene polyol is neutralized in the order of [1] and [2].
In the first stage [1], water is added to the first crude polyoxyalkylene polyol (d), followed by normal heat treatment, followed by liquid separation using a liquid / liquid separator. The amount of water added in [1] is preferably 2 to 12% by weight, more preferably 3 to 10% by weight, based on the first crude polyoxyalkylene polyol (d). If it is 2% by weight or more, the alcoholate of the polyether can be sufficiently hydrolyzed, and the liquid / liquid separation ability is not lowered and the separation time is not significantly increased. When the content is 12% by weight or less, water is sufficiently emulsified in the polyether, so that the separation performance is good and the liquid can be separated in a short time, and the amount of drainage is suppressed.

The heating temperature is preferably 70 to 150 ° C, more preferably 100 to 130 ° C. When the temperature is 70 ° C. or higher, the separating ability is increased, and when the temperature is 150 ° C. or lower, the quality of the polyether is not deteriorated. The heating time is preferably 1 to 10 minutes.
Examples of the liquid / liquid separator include commercially available multilayer filter separators, centrifugal separators, and the like, but a method using a multilayer filter separator is preferred from the viewpoint of continuous productivity. Multi-layer filter separation device is a pre-filter (function to remove solid foreign matter), coalescer (function to combine fine droplet particles dispersed by passing fluid through this medium), separator (specific gravity) This is a separation apparatus having three functions (settlement separation of a droplet having a high specific gravity due to the difference). The material of the filter is not particularly limited. For example, fluororesins such as polypropylene and polytetrafluoroethylene, polyesters, polyphenylene sulfide, acrylics, meta-aramids and the like can be mentioned. From the viewpoint of heat resistance temperature, fluororesins such as polytetrafluoroethylene are preferable.
As for the separation conditions when a multilayer filter is used, the temperature is preferably 70 to 150 ° C, more preferably 100 to 130 ° C. For example, it can be separated by passing through a filter at a flow rate of 1,000 to 8,000 m ³ / h. The end point of the separation operation may be that the polyether layer is transparent.
Since the centrifugal separator only increases the separation speed of oil and water, it may be vertical or horizontal, and the separation conditions are preferably those with a rotational speed of 100 rpm or more, and preferably the temperature is 70 to 150. C., time is 5 to 20 minutes, and after centrifugation, it can be suitably separated by allowing to stand for 30 to 60 minutes. In this case, the polyether is the upper layer and the water is the lower layer. By discharging the lower layer water, the upper polyether layer is obtained as the second crude polyoxyalkylene polyol (f).

  The residual base concentration in the second crude polyoxyalkylene polyol (f) can be measured based on the CPR measurement method in Section 6.8 of JIS K1557 [Polyurethane Polyether Test Method], and is preferably 500 or less. More preferably, it is 300 or less, Most preferably, it is 100 or less. When the CPR of the second crude polyoxyalkylene polyol (f) is 500 or less, the time required for neutralization with an acid in the stage [2] is short, which is efficient.

  In step [2] of the production method of the present invention, the second crude polyoxyalkylene polyol (f) obtained in [1] is neutralized in two steps with a weak acid (g) and then with a strong acid (h), and then dehydrated. It is a process.

The acidity of an acidic compound is generally represented by an acid dissociation index pKa in water (see Chemical Handbook). In general, a pKa of 2 or less is a strong acid, and a pKa of 3 or more is a weak acid.
The weak acid (g) used in the present invention preferably has a pKa of 3.5 to 13, particularly 7 to 12.
Such weak acids (g) include lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, lithium monohydrogen phosphate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, lithium hydrogen sulfate, sodium hydrogen sulfate, hydrogen sulfate. Inorganic acid acidic salts such as potassium, lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; inorganic weak acids such as hypochlorous acid, hypobromite, hypoiodous acid, boric acid and carbonic acid; formic acid, acetic acid and propionic acid Organic carboxylic acids having 1 to 22 carbon atoms such as succinic acid, citric acid, tartaric acid, fumaric acid, malic acid; phenol, cresol, nitrophenol, 2,6-dimethylphenol, 2,6-diethylparacresol and 2, 6-di-tert-butylparacresol, tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4 ′ Hydroxyphenyl) propionate) methane, octadecyl-3 ', 5'-di -tert- butyl-4'-hydroxyphenyl) phenol group-containing compounds such as propionate; and the like. Among these, a phenol group-containing compound is preferable, and 2,6-di-tert-butylparacresol, tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-) is more preferable. Hydroxyphenyl) propionate) methane, and octadecyl-3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

  As strong acid (h), mineral acids such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, phosphorous acid, hypophosphorous acid and chlorous acid; organic acids such as alkylbenzenesulfonic acid and dodecylbenzenesulfonic acid; Can be mentioned. Of these, mineral acids are preferred, and phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid are more preferred. Salts generated from these acids are easily crystallized and easily removed by filtration or the like.

  The amount of acidic protons in the weak acid (g) used in the production method of the present invention is 1.00 to 10 mol with respect to 1 mol of the remaining alkali metal catalyst (a) in the second crude polyoxyalkylene polyol (f). preferable. More preferably, it is 1.00-5 mol. If it is 1.00 mol or more, all remaining alkali catalysts can be neutralized, and if it is 10 mol or less, the performance of the polyoxyalkylene polyol is not affected.

The amount of acidic protons in the strong acid (h) used in the production method of the present invention is 1.00 to 10 mol per 1 mol of the remaining alkali metal catalyst (a) in the second crude polyoxyalkylene polyol (f). preferable. More preferably, it is 1.00-5 mol. When the amount is 1.00 mol or more, neutralization proceeds completely, and when the amount is 10 mol or less, the performance of the polyoxyalkylene polyol is not affected at all.
Moreover, the acid value after (h) addition can be measured based on the acid value measuring method of Section 6.6 of JIS K1557 [Polyether test method for polyurethane], and is preferably 3.0 or less. More preferably, it is 1.0 or less. When the acid value is 3.0 or less, the reactivity with isocyanate can be used without decreasing.

The temperature at which the weak acid (g) and the strong acid (h) are added to the second crude polyoxyalkylene polyol (f) is preferably 70 to 130 ° C, more preferably 90 to 120 ° C. When it is 70 ° C. or higher, the neutralization rate is high, and when it is 130 ° C. or lower, the quality of the polyether is not deteriorated. The stirring time after adding the weak acid (g) is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, and particularly preferably 15 minutes to 3 hours. If it is 1 minute or longer, the added acid can be uniformly dispersed in the liquid, and if it is 6 hours or less, the neutralization reaction proceeds sufficiently and the production efficiency does not decrease. The strong acid (h) is added after the weak acid (g) is uniformly dispersed by stirring. The stirring time after adding the strong acid (h) is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, and particularly preferably 15 minutes to 3 hours. If it is 1 minute or longer, the added acid can be uniformly dispersed in the liquid, and if it is 6 hours or less, the neutralization reaction proceeds sufficiently and the production efficiency does not decrease.
The strong acid (h) may be added before the neutralization reaction with the weak acid (g) is completed.

The obtained second crude polyoxyalkylene polyol (f) is dehydrated at 90 to 160 ° C. under reduced pressure (0 to 100 kPa), for example. As a method, a batch method or a shower ring method may be used. By this dehydration, the neutralized salt (e) resulting from the reaction between the alkali metal catalyst (a) and the acid is precipitated.
The amount of the neutralized salt (e) to be precipitated is preferably 1% by weight or less, more preferably 0.5% by weight or less, based on the second crude polyoxyalkylene polyol (f). If it is 1% by weight or less, the subsequent addition polymerization of the alkylene oxide (c) in the presence of the acidic catalyst (j) easily proceeds. The production method of the present invention is preferably carried out in the absence of oxygen, and is carried out at a gas phase oxygen concentration of preferably 1000 ppm or less, more preferably 500 ppm or less through the steps [1] and [2]. If it is 1000 ppm or less, the polyether is hardly oxidized, and as a result, it is difficult to be colored. The method for reducing the oxygen concentration is preferably carried out by introducing an inert gas such as nitrogen gas or argon gas into the reaction apparatus.

By continuously carrying out the steps [1] and [2], a composition (P) comprising a neutralized salt (e), a weak acid (g) and a polyoxyalkylene polyol can be obtained.
The weak acid (g) and the strong acid (h) that are excessively present in (P) may be removed by treatment with an acid adsorbent.
The amount of the weak acid (g) in the composition (P) comprising the neutralized salt (e), the weak acid (g) and the polyoxyalkylene polyol is preferably from 0.00001 to 1% by weight, more preferably 0.0001. ~ 0.5 wt%. If it is 0.00001% by weight or more, the reaction between the weak acid salt and the strong acid proceeds completely, and if it is 1% by weight or less, the alkylene oxide (c) in the presence of the acidic catalyst (j) to be subsequently carried out ) Proceeds easily.
The amount of the strong acid (h) in (P) is preferably 0.5% by weight or less, and more preferably 0.1% by weight or less. If it is 0.5% by weight or less, the subsequent addition polymerization of the alkylene oxide (c) under the acidic catalyst (j) proceeds easily.
The amount of the neutralized salt (e) in (P) is preferably 0.00001 to 1% by weight, more preferably 0.00005 to 0.5% by weight. When neutralization with the weak acid (g) and the strong acid (h) is completely advanced, the amount of the neutralized salt (e) is 0.00001% by weight or more, and if it is 1% by weight or less, the subsequent acidity Addition polymerization of the alkylene oxide (c) easily proceeds in the presence of the catalyst (j).

Preferred examples of the acid adsorbent include hydrotalcite-based adsorbents (for example, Kyoward 500, Kyoward 1000, Kyoward 2000, etc. <all manufactured by Kyowa Chemical Industry Co., Ltd.>) and the like. The amount of the acid adsorbent is preferably 0.05 to 0.2% by weight based on the crude polyether. The average particle size of the hydrotalcite-based adsorbent is preferably 10 to 100 μm. When it is 10 μm or more, the filtration rate is fast and the production capacity is good. When it is 100 μm or less, the adsorptive power does not decrease and the neutralized salt (e) and the acid do not elute.
The filtration may be either pressure filtration or vacuum filtration, but pressure filtration is preferred because it is easy to prevent oxygen contamination. The material of the filter is not particularly limited. For example, paper, polypropylene, polytetrafluoroethylene, polyester, polyphenylene sulfide, acrylic, meta-aramid and the like can be mentioned, but paper is preferable. The retained particle diameter of the filter is preferably 0.1 to 10 μm, and more preferably 1 to 5 μm.

  A polyoxyalkylene polyol composition (P) is added with an acidic catalyst (j) and subjected to addition polymerization of an alkylene oxide (c) to form a polyoxyl comprising a neutralized salt (e), a weak acid (g) and a polyoxyalkylene polyol. An alkylene polyol composition (Q) is obtained.

As the acidic catalyst (j) used in the present invention, a known double metal cyanide (DMC) catalyst (j1) can be used, and its composition is not particularly limited.
(J1) is usually a reaction product of a water-soluble metal salt and a water-soluble metal cyanide salt. The water-soluble metal salt is preferably represented by the general formula M ₁ Qn, and M ₁ includes Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II ), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (III), V (V), V (IV), Sr (II), W (IV), W (VI ), Cu (II), Cr (III) and the like. Preferred are Zn (II), Fe (II), Co (II), and Ni (II). In the above formula, Q is a halide ion, hydroxide ion, sulfate ion, carbonate ion, cyanide ion, oxalate ion, thiocyanate ion, isocyanate ion, isothiocyanate ion, carboxylate ion, and nitrate ion. Etc. n is 1-3. Examples of metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetonyl acetate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt thiocyanate (II), nickel (II) formate, nickel (II) nitrate, and a mixture thereof.
The water-soluble metal cyanide salt is preferably represented by the general formula (M ′) a M ₂ (CN) b (A) c, where M ₂ is Fe (II), Fe (III), Co (II) , Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) , And V (V). Preferred are Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III), and Ni (II). The water-soluble metal cyanide salt can contain one or more of these metals. In the above formula, M ′ is an alkali metal ion or an alkaline earth metal ion. Examples of A include the same as Q. a and b are both 1 or an integer larger than 1, and the sum of charges of a, b and c is equal to the charge of M ₂ . Examples of water-soluble metal cyanide salts include potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanoiridate (III ) And the like.

Specific examples of the double metal cyanide (DMC) catalyst (j1) include zinc hexacyanocobaltate (III), zinc hexacyanoferrate (III), zinc hexacyanoferrate (II), nickel (II) hexacyanoferrate (II ), Cobalt (II) hexacyanocobaltate (III), etc., preferably zinc hexacyanocobaltate (III).
In addition, DMC catalysts described in JP-A-10-36500 and US Pat. No. 5,158,922 can also be used.

  Regarding the addition conditions of the alkylene oxide (c), a method that is usually performed may be used. For example, it is preferably 0.0001 to 10% by weight, more preferably 0.001 to 1% by weight, based on the ring-opened polymer to be formed. (J1) is preferably used at 0 to 250 ° C., more preferably 50 to 180 ° C.

In the present invention, as the acidic catalyst (j), one or more compounds (j2) selected from the group consisting of compounds represented by the following general formula (1), general formula (2), and general formula (3) ) Can also be used.
XT ₃ (1)

F
｜
XT ₂ (2)

F ₂
｜
XT (3)
[In the formulas (1), (2) and (3), X represents a boron atom or an aluminum atom; F represents a fluorine atom; T represents a (substituted) phenyl represented by the following general formula (4) Represents a group and / or a tertiary alkyl group represented by the following general formula (5), and when there are a plurality of T, the plurality of T may be the same or different. ]

[In Formula (4), Z represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group. k represents an integer of 0 to 5, and when k is 2 or more, the plurality of Z may be the same or different from each other. ]
R ₁
｜
-C-R ₂ (5)
｜
R ₃
[In Formula (5), R < ₁ >, R < ₂ >, R < ₃ > represents a C1-C4 alkyl group each independently. ]

Of Z in the general formula (4), preferred are a hydrogen atom, a halogen atom and a cyano group, and more preferred are a halogen atom and a cyano group. Specific examples of the phenyl group or substituted phenyl group represented by the general formula (4) include a phenyl group, a pentafluorophenyl group, a p-methylphenyl group, a p-cyanophenyl group, and a p-nitrophenyl group. Preferred are a phenyl group, a pentafluorophenyl group, and a p-cyanophenyl group, and more preferred are a phenyl group and a pentafluorophenyl group.
Specific examples of R ₁ , R ₂ and R _{3 in} the general formula (5) include a methyl group, an ethyl group, a propyl group and an isopropyl group. Specific examples of the tertiary alkyl group represented by the general formula (5) include a t-butyl group and a t-pentyl group.

Specific examples of these (j2) include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris ( Pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, bis (pentafluorophenyl) fluoroborane, di (t -Butyl) borane fluoride, (pentafluorophenyl) difluoride borane, (t-butyl) difluoroborane, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluoro Phenyl) difluoride Chloride, and the like (t-butyl) 2 aluminum fluoride.
Of these, preferred are triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum, and more preferred are tris (pentafluorophenyl) borane and tris (pentafluoro). It is at least one selected from phenyl) aluminum.

  Regarding the addition conditions of the alkylene oxide (c), a method that is usually performed may be used. For example, it is preferably 0.0001 to 10% by weight, more preferably 0.001 to 1% by weight, based on the ring-opened polymer to be formed. (J2) is preferably used at 0 to 250 ° C, more preferably 20 to 180 ° C.

In the present invention, it is preferable to use (j1) or (j2) as the acidic catalyst (j), but other acidic catalysts may be used. Other acidic catalysts include BF ₃ ; scandium catalysts such as scandium (III) triflate, scandium (III) trifurylimide, scandium (III) trifurylmethide; titanium (III) chloride, titanium (IV) chloride, tetra (i- Propoxy) titanium catalysts such as titanium (IV); tin catalysts such as tin (IV) chloride; and the like.

The content of the weak acid (g) in the polyoxyalkylene polyol composition (Q) is preferably 0.00001 to 1% by weight, more preferably 0.0001 to 0.5% by weight, based on (Q). It is. When the amount is 0.00001% by weight or more, the reaction between the weak acid salt and the strong acid in the previous step is completely advanced, and when the amount is 1% by weight or less, the polyoxyalkylene polyol composition (R) is used. The elongation property of the resin is good.
The amount of the neutralized salt (e) in (Q) is preferably 0.00001 to 1% by weight, more preferably 0.00005 to 0.5% by weight. When neutralization with the weak acid (g) and the strong acid (h) is completely advanced, the amount of the neutralized salt (e) is 0.00001% by weight or more, and if it is 1% by weight or less, the polyoxyalkylene polyol The elongation property of the resin produced using the composition (Q) is good.

By removing the neutralized salt (e) in the polyoxyalkylene polyol composition (Q) obtained by addition polymerization of the alkylene oxide (c) in the presence of the acidic catalyst (j) by filtration, and then dehydrating as necessary. A polyoxyalkylene polyol composition (R) comprising a weak acid (g) and a polyoxyalkylene polyol is obtained. According to the production method of the present invention, a polyoxyalkylene polyol composition (R) comprising a weak acid (g) and a polyoxyalkylene polyol each having a residual alkali metal catalyst (a) and a content of neutralized salt (e) of 1 ppm or less. Can be easily obtained.
The content of the weak acid (g) is preferably 0.00001 to 1% by weight, more preferably 0.0001 to 0.5% by weight, based on the weak acid (g) -containing polyoxyalkylene polyol composition (R). It is. When the content is 1% by weight or less, the elongation property of the resin produced using the polyoxyalkylene polyol composition (R) is good.

The neutralized salt (e) may be filtered by any method known in the art. For example, the above-mentioned hydrotalcite-based adsorbents (for example, Kyward 500, Kyward 1000, Kyward 2000 etc. <all manufactured by Kyowa Chemical Industry Co., Ltd.>) and filter aids such as diatomaceous earth (eg, Radiolite 600, Radio Light 800, Radiolite 900 <both manufactured by Showa Chemical Industry Co., Ltd.>) and the like can be used. The filtration may be either pressure filtration or vacuum filtration, but pressure filtration is preferred because it is easy to prevent oxygen contamination. The material of the filter is not particularly limited. For example, paper, polypropylene, polytetrafluoroethylene, polyester, polyphenylene sulfide, acrylic, meta-aramid and the like can be mentioned, but paper is preferable. The retained particle diameter of the filter is preferably 0.1 to 10 μm. Furthermore, the thing of 1-5 micrometers is preferable.
When the water content is high, the dehydration is subsequently performed at 90 to 160 ° C. under reduced pressure (100 kPa or less). As a method, a batch method or a shower ring method may be used.
This step is also preferably performed in the absence of oxygen, and the oxygen concentration is preferably 1000 ppm or less, more preferably 500 ppm or less. If it is 1000 ppm or less, the polyether is difficult to be oxidized, and as a result, it is difficult to be colored. It is desirable to reduce the oxygen concentration by passing an inert gas such as nitrogen gas or argon gas into the filtration device.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, the part in an Example is a weight part.
In the examples, the pH was measured by the method of 6.9 of JIS K1557 [Polyurethane Polyether Test Method] [about 14% by volume of isopropyl alcohol / water (10/6 volume ratio) mixture]. The hydroxyl value was measured based on the hydroxyl value measurement method in 6.4 of the JIS test method. The water content was measured by the Karl Fischer method described in 6.5 of the JIS test method. The acid value was measured by the potentiometric titration method in Section 6.6 of the JIS test method. The residual base concentration was measured based on the CPR measurement method in Section 6.8 of the JIS test method and converted as an alkali metal hydroxide. The primary OH conversion rate of the terminal hydroxyl group is calculated by ¹ H-NMR method after pre-treatment of the sample in advance. Details of the ¹ H-NMR method will be specifically described below.

<Sample preparation method>
About 30 mg of a measurement sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added and the mixture is allowed to stand at 25 ° C. for about 5 minutes to make the polyol a trifluoroacetic acid ester, which is used as an analytical sample.

  Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.

<Calculation method of primary OH ratio of terminal hydroxyl group>
The signal derived from the methylene group to which the primary hydroxyl group is bonded is observed at around 4.3 ppm, and the signal derived from the methine group to which the secondary hydroxyl group is bonded is observed at around 5.2 ppm. Is calculated by the following formula.

Primary OH conversion rate (%) = [r / (r + 2s)] × 100
However,
r: integral value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm s: integral value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm

<Production Example 1>
The autoclave was charged with 92 parts of glycerin and 11 parts of potassium hydroxide, vacuum-dehydrated at 120 ° C. for 60 minutes after substitution with nitrogen. Subsequently, the temperature is raised to 100 to 110 ° C., 4400 parts of propylene oxide is injected in about 3 hours, and the volatile content is 0.1% by weight or less (measured by reacting the acid and back titrating the unreacted acid. The reaction was continued for 2 hours at the same temperature until the first crude polyoxyalkylene polyol (d-1) was obtained. The first crude polyoxyalkylene polyol (d-1) had a potassium hydroxide concentration of 2,500 ppm and a CPR of 1340.

<Production Example 2>
An autoclave was charged with 76 parts of 1,2-propylene glycol and 7.7 parts of potassium hydroxide, purged with nitrogen and vacuum dehydrated at 120 ° C. for 60 minutes. Next, the temperature is raised to 100 to 110 ° C., 3124 parts of propylene oxide is injected in about 3 hours, and the volatile content is 0.1% by weight or less (measured by reacting the acid and back-titration of the unreacted acid. The reaction was continued for 2 hours at the same temperature until the first crude polyoxyalkylene polyol (d-2) was obtained. The first crude polyoxyalkylene polyol (d-2) had a potassium hydroxide concentration of 2,500 ppm and a CPR of 1340.

<Example 1>
85 parts of tap water (8.5% by weight with respect to the first crude polyoxyalkylene polyol) was added to 1000 parts of the first crude polyoxyalkylene polyol (d-1) obtained in Production Example 1, and the air was purged with nitrogen. Liquid / liquid separation device with a multi-layer filter consisting of a prefilter, coalescer and separator at 120 ° C (product of Nippon Pall Co., Ltd., product) (Name: Phase Sep Coalreser), water washing / polyether liquid separation was performed, and the aqueous phase was removed to obtain a second crude polyoxyalkylene polyol (f-1). (F-1) had a colorless and transparent appearance, CPR was 21 ppm, and water was 2.7% by weight.
1,000 parts of the second crude polyoxyalkylene polyol (f-1) was placed in a 10 liter autoclave and purged with nitrogen, followed by Irganox 1010 (tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl). -4′-hydroxyphenyl) propionate) methane, manufactured by Ciba Specialty Chemicals, pKa10) (0.3 parts of acidic protons per 1 mole of alkali metal catalyst) was added and stirred at 90 ° C. for 30 minutes. . Subsequently, 0.056 parts of 62% by weight aqueous sulfuric acid solution (1.01 mol of acidic protons per 1 mol of alkali metal catalyst) was added. The mixture was stirred at 90 ° C. for 3 hours and then dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (P-1) composed of Irganox 1010, potassium sulfate, and polyoxyalkylene polyol. The pH of the polyol composition (P-1) was 6.6, and the acid value was 0.1 or less.

<Example 2>
4000 parts of the polyol composition (P-1) was placed in a 10 liter autoclave, charged with 1 part of zinc hexacyanocobaltate (III) (DMC catalyst), purged with nitrogen, heated to 100-110 ° C., and then propylene 2000 parts of oxide was injected over about 3 hours. The reactor pressure decreased with the addition of propylene oxide, indicating that propylene oxide was reacting. The reaction was continued for 2 hours at the same temperature until the volatile content was 0.1% by weight or less (measured by reacting the acid and back-titration of the unreacted acid). Irganox 1010, potassium sulfate and polyoxyalkylene A polyol composition (Q-1) comprising a polyol was obtained.
Using a stainless steel pressure filter (diameter: 12.5 cm, height: 9 cm), no. Pressure (0.1 MPa) filtration was performed under nitrogen with 2 filter paper (manufactured by Toyo Roshi Kaisha). The filtrate was dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (R-1) composed of colorless and transparent (Hazen unit color number 10) Irganox 1010 and a polyoxyalkylene polyol. The residual base concentration of (R-1) was 0.2 ppm, and the neutralized salt (e) was not detected. (The neutralized salt was measured by measuring the alkali metal concentration with an ICP emission spectrophotometer. It was calculated by the difference. The hydroxyl value of the polyol composition (R-1) was 28, the primary OH conversion rate was 2%, and the acid value was 0.1 or less.

<Example 3>
After 4000 parts of the polyol composition (P-1) was put into a 10 liter autoclave, 0.2 parts of tris (perfluorophenyl) borane was charged and purged with nitrogen, the temperature was raised to 70 to 80 ° C., and then propylene oxide 700 The part was pressed in over about 3 hours. The reactor pressure decreased with the addition of propylene oxide, indicating that propylene oxide was reacting. The reaction was continued for 2 hours at the same temperature until the volatile content was 0.1% by weight or less (measured by reacting the acid and back-titration of the unreacted acid). Irganox 1010, potassium sulfate and polyoxyalkylene A polyol composition (Q-2) comprising a polyol was obtained.
Using a stainless steel pressure filter (diameter: 12.5 cm, height: 9 cm), no. Pressure (0.1 MPa) filtration was performed under nitrogen with 2 filter paper (manufactured by Toyo Roshi Kaisha). The filtrate was dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (R-2) composed of colorless and transparent (Hazen unit color number 10) Irganox 1010 and a polyoxyalkylene polyol. The residual base concentration of (R-2) was 0.2 ppm, and no neutralized salt was detected (measurement of the neutralized salt was performed by measuring the alkali metal concentration with an ICP emission spectrophotometer, and the difference from the alkaline content of the residual base. ). The hydroxyl value of the polyol composition (R-2) was 39, the primary OH conversion rate was 70%, and the acid value was 0.1 or less.

<Comparative Example 1>
After 1,000 parts of the first crude polyoxyalkylene polyol (d-1) was placed in a 10 liter autoclave and purged with nitrogen, 3.59 parts of 62 wt% sulfuric acid aqueous solution (1.01 mole per mole of alkali metal catalyst). ) And stirred at 90 ° C. for 30 minutes. Subsequently, 25 parts of water was added and stirred for 3 hours, followed by dehydration at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (N-1) comprising potassium sulfate and polyoxyalkylene polyol. The pH of the polyol composition (N-1) was 6.6, and the acid value was 0.1 or less.

<Comparative example 2>
4000 parts of the polyol composition (N-1) was placed in a 10 liter autoclave, charged with 1 part of zinc hexacyanocobaltate (III) (DMC catalyst), purged with nitrogen, heated to 100-110 ° C., and then propylene Attempts were made to inject oxide, but no reduction in the reactor internal pressure was observed, making it impossible to carry out.

<Comparative Example 3>
4,000 parts of the polyol composition (N-1) was put in a 10 liter autoclave, 0.2 part of tris (perfluorophenyl) borane was charged, and after nitrogen substitution, the temperature was raised to 70 to 80 ° C., and then propylene oxide Although press-fitting was attempted, the pressure inside the reactor was not lowered and could not be carried out.

<Comparative Example 4>
1,000 parts of the second crude polyoxyalkylene polyol (f-1) obtained in Example 1 was placed in a 10 liter autoclave and purged with nitrogen, and then 0.056 parts of 62 wt% sulfuric acid aqueous solution (alkali metal catalyst 1 1.01 moles of acidic protons per mole) was added. The mixture was stirred at 90 ° C. for 3 hours and dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (O-1) comprising potassium sulfate and polyoxyalkylene polyol. The pH of the polyol (O-1) was 6.8, and the acid value was 0.1 or less.

<Comparative Example 5>
4000 parts of the polyol composition (O-1) was put in a 10 liter autoclave, 1 part of zinc hexacyanocobaltate (III) (DMC catalyst) was charged, and the atmosphere was purged with nitrogen. Attempts were made to inject oxide, but no reduction in the reactor internal pressure was observed, making it impossible to carry out.

<Comparative Example 6>
4,000 parts of the polyol composition (O-1) was put into a 10 liter autoclave, 0.2 part of tris (perfluorophenyl) borane was charged, and after nitrogen substitution, the temperature was raised to 70 to 80 ° C., and then propylene oxide Although press-fitting was attempted, the pressure inside the reactor was not lowered and could not be carried out.

<Example 4>
95 parts of tap water (9.5 wt% with respect to the first crude polyoxyalkylene polyol) was added to 1000 parts of the first crude polyoxyalkylene polyol (d-2) obtained in Production Example 2, and gas was removed by nitrogen substitution. Liquid / liquid separation device with a multi-layer filter consisting of a prefilter, coalescer and separator at 120 ° C (product of Nippon Pall Co., Ltd., product) Name: Phase Sep Coalreser), water washing / polyether liquid separation was performed, and the aqueous phase was removed to obtain a second crude polyoxyalkylene polyol (f-2). (F-2) had a colorless and transparent appearance, CPR was 76 ppm, and water content was 4.0% by weight.
After 1,000 parts of the second crude polyoxyalkylene polyol (f-2) was placed in a 10 liter autoclave and purged with nitrogen, Irganox 1076 (octadecyl-3 ′, 5′-di-tert-butyl-4′-hydroxy 5 parts of phenyl) propionate, manufactured by Ciba Specialty Chemicals, pKa10) (3.7 mol of acidic protons per 1 mol of alkali metal catalyst) were added, and the mixture was stirred at 90 ° C. for 30 minutes. Next, 0.44 parts of 90 wt% aqueous phosphoric acid solution (4.8 mol of acidic protons per 1 mol of alkali metal catalyst) was added. The mixture was stirred at 90 ° C. for 3 hours and then dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (P-2) comprising Irganox 1076, potassium phosphate and polyoxyalkylene polyol. The pH of the polyol composition (P-2) was 5.6, and the acid value was 0.5.

<Example 5>
3200 parts of the polyol composition (P-2) was placed in a 10 liter autoclave, charged with 1 part of zinc hexacyanocobaltate (III) (DMC catalyst), purged with nitrogen, heated to 100-110 ° C, and then propylene 2800 parts of oxide was injected over about 3 hours. The reactor pressure decreased with the addition of propylene oxide, indicating that propylene oxide was reacting. The reaction was continued for 2 hours at the same temperature until the volatile content was 0.1% by weight or less (measured by reacting the acid and back-titration of the unreacted acid). Irganox 1076, potassium phosphate and polyoxy A polyol composition (Q-3) comprising an alkylene polyol was obtained.
Using a stainless steel pressure filter (diameter: 12.5 cm, height: 9 cm), no. Pressure (0.1 MPa) filtration was performed under nitrogen with 2 filter paper (manufactured by Toyo Roshi Kaisha). The filtrate was dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (R-3) comprising Irganox 1076 which was colorless and transparent (hazen unit color number 10) and polyoxyalkylene polyol. The residual base concentration of (R-3) was 0.1 ppm, and no neutralized salt was detected. (The neutralized salt was measured by measuring the alkali metal concentration with an ICP emission spectrophotometer, and the difference from the alkaline content of the residual base. ). The hydroxyl value of the polyol composition (R-3) was 19, the primary OH conversion rate was 1%, and the acid value was 0.4.

<Example 6>
3200 parts of the polyol composition (P-2) was put into a 10 liter autoclave, 0.2 part of tris (perfluorophenyl) borane was charged, and the atmosphere was replaced with nitrogen. Then, the temperature was raised to 70 to 80 ° C., and then propylene oxide 400 The part was pressed in over about 3 hours. The reactor pressure decreased with the addition of propylene oxide, indicating that propylene oxide was reacting. The reaction was continued for 2 hours at the same temperature until the volatile content was 0.1% by weight or less (measured by reacting the acid and back-titration of the unreacted acid). Irganox 1076, potassium phosphate and polyoxy A polyol composition (Q-4) comprising an alkylene polyol was obtained.
Using a stainless steel pressure filter (diameter: 12.5 cm, height: 9 cm), no. Pressure (0.1 MPa) filtration was performed under nitrogen with 2 filter paper (manufactured by Toyo Roshi Kaisha). The filtrate was dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (R-4) composed of colorless and transparent (hazen unit color number 10) Irganox 1076 and polyoxyalkylene polyol. The residual base concentration of (R-4) was 0.2 ppm, and no neutralized salt was detected (the neutralized salt was measured by measuring the alkali metal concentration with an ICP emission spectrophotometer, and the difference from the alkaline content of the residual base. ). The resulting polyol composition (R-4) had a hydroxyl value of 32, a primary OH conversion rate of 68%, and an acid value of 0.4.

<Comparative Example 7>
After 1,000 parts of the first crude polyoxyalkylene polyol (d-2) was placed in a 10 liter autoclave and purged with nitrogen, 2.1 parts of a 90 wt% aqueous phosphoric acid solution (1.3 parts per mole of alkali metal catalyst). Mol) and the mixture was stirred at 90 ° C. for 30 minutes. Subsequently, 25 parts of water was added and stirred for 3 hours, followed by dehydration at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (N-2) comprising potassium phosphate and polyoxyalkylene polyol. The pH of this mixture was 4.1 and the acid value was 0.8.

<Comparative Example 8>
3200 parts of the polyol composition (N-2) was placed in a 10 liter autoclave, charged with 1 part of zinc hexacyanocobaltate (III) (DMC catalyst), purged with nitrogen, heated to 100-110 ° C., and then propylene Attempts were made to inject oxide, but no reduction in the reactor internal pressure was observed, making it impossible to carry out.

<Comparative Example 9>
3200 parts of the polyol composition (N-2) was placed in a 10 liter autoclave, charged with 0.2 parts of tris (perfluorophenyl) borane, purged with nitrogen, heated to 70-80 ° C., and then propylene oxide. Although press-fitting was attempted, the pressure inside the reactor was not lowered and could not be carried out.

<Comparative Example 10>
1,000 parts of the second crude polyoxyalkylene polyol (f-2) obtained in Example 4 was placed in a 10 liter autoclave and purged with nitrogen, and then 0.36 parts of 90 wt% phosphoric acid aqueous solution (alkali metal catalyst). 4.0 mol of acidic proton was added to 1 mol). The mixture was stirred at 90 ° C. for 3 hours and dehydrated at 130 ° C. under reduced pressure (20 Torr) for 1 hour to obtain a polyol composition (O-2) composed of potassium phosphate and polyoxyalkylene polyol. The pH of this mixture was 5.5, and the acid value was 0.2.

<Comparative Example 11>
3200 parts of the polyol composition (O-2) was placed in a 10 liter autoclave, charged with 1 part of zinc hexacyanocobaltate (III) (DMC catalyst), purged with nitrogen, heated to 100-110 ° C., and then propylene Attempts were made to inject oxide, but no reduction in the reactor internal pressure was observed, making it impossible to carry out.

<Comparative Example 12>
3200 parts of the polyol composition (O-2) was placed in a 10 liter autoclave, charged with 0.2 part of tris (perfluorophenyl) borane, purged with nitrogen, heated to 70-80 ° C., and then propylene oxide Although press-fitting was attempted, the pressure inside the reactor was not lowered and could not be carried out.

  The polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide in the presence of an alkali metal catalyst obtained by the production method of the present invention is neutralized with a weak acid and a strong acid, and then the alkylene oxide is subjected to addition polymerization in the presence of an acidic compound. The obtained polyoxyalkylene polyol composition is useful as various raw materials such as a raw material for flexible polyurethane foam, a raw material for rigid polyurethane foam, and a raw material for urethane adhesive.

Claims (11)

A first crude polyoxyalkylene polyol (d) obtained by addition polymerization of an alkylene oxide (c) to an active hydrogen-containing compound (b) in the presence of an alkali metal catalyst (a) in the following order [1] [2] A process for producing a polyoxyalkylene polyol composition (P) comprising a neutralized salt (e), a weak acid (g), and a polyoxyalkylene polyol, which is characterized by being treated.
[1] Water is added to the first crude polyoxyalkylene polyol (d), and after liquid separation using a liquid / liquid separator, the aqueous phase is removed to obtain the second crude polyoxyalkylene polyol (f).
[2] The second crude polyoxyalkylene polyol (f) is neutralized in two stages with a weak acid (g) and then with a strong acid (h), and then dehydrated to obtain (P). The production method according to claim 1, wherein the weak acid (g) has a pKa of 3.5 to 13. The process according to claim 1 or 2, wherein the weak acid (g) is a phenol group-containing compound. The method according to any one of claims 1 to 3, wherein the strong acid (h) is a mineral acid. The amount of acidic protons in the weak acid (g) is 1.00 to 10 mol per 1 mol of the remaining alkali metal catalyst (a) in the second crude polyoxyalkylene polyol (f). Any manufacturing method. The amount of acidic protons in the strong acid (h) is 1.00 to 10 mol per 1 mol of the remaining alkali metal catalyst (a) in the second crude polyoxyalkylene polyol (f). Any manufacturing method. Neutralized salt (e), wherein an acidic catalyst (j) is added to the polyoxyalkylene polyol composition (P) obtained by the production method according to any one of claims 1 to 6 to effect addition polymerization of the alkylene oxide (c). , A method for producing a polyoxyalkylene polyol composition (Q) comprising a weak acid (g) and a polyoxyalkylene polyol. The process according to claim 7, wherein the acidic catalyst (j) is a double metal cyanide (DMC) catalyst (j1). The acidic catalyst (j) is one or more selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3) The production method according to claim 7, wherein the compound (j2) is:
XT ₃ (1)

F
｜
XT ₂ (2)

F ₂
｜
XT (3)
[In the formulas (1), (2) and (3), X represents a boron atom or an aluminum atom; F represents a fluorine atom; T represents a (substituted) phenyl represented by the following general formula (4) Represents a group and / or a tertiary alkyl group represented by the following general formula (5), and when there are a plurality of T, the plurality of T may be the same or different. ]
[In Formula (4), Z represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group. k represents an integer of 0 to 5, and when k is 2 or more, the plurality of Z may be the same or different from each other. ]
R ₁
｜
-C-R ₂ (5)
｜
R ₃
[In Formula (5), R < ₁ >, R < ₂ >, R < ₃ > represents a C1-C4 alkyl group each independently. ] A polyacid comprising a weak acid (g) and a polyoxyalkylene polyol, wherein the neutralized salt (e) in the polyoxyalkylene polyol composition (Q) obtained by the production method according to any one of claims 7 to 9 is removed by filtration. The manufacturing method of an oxyalkylene polyol composition (R). A polyoxyalkylene polyol obtained by the production method according to claim 10 and comprising a weak acid (g) having a residual alkali metal catalyst (a) and a neutralized salt (e) content of 1 ppm or less and a polyoxyalkylene polyol. Composition (R).