JP2010077417A - Method for producing polyoxyalkylene alcohol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To find a method for producing a polyoxyalkylene alcohol having particularly improved odor without requiring a post-treatment step for removing low boiling point volatile components.
In a reaction tank (1), a by-product low-boiling compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa is continuously or intermittently removed from the system in the presence of a Lewis acid catalyst (a). The method of addition polymerization of the alkylene oxide (d) to the active hydrogen-containing compound (c) while removing, wherein the method of continuously or intermittently removing (b) out of the system is a reaction tank (1 ) Is a method for continuously or intermittently removing the gas phase from the system.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a polyoxyalkylene alcohol and a method for producing a polyurethane resin using the same.

  Usually, polyoxyalkylene alcohols use alkali metals such as potassium hydroxide, Lewis acids such as aluminum chloride and boron trifluoride as catalysts, and propylene oxide (hereinafter abbreviated as PO) or ethylene oxide as an active hydrogen-containing compound. (Hereinafter abbreviated as EO) and the like, and obtained by addition polymerization of alkylene oxide.

  Among them, polyoxyalkylene alcohols produced using a Lewis acid catalyst contain by-product low-boiling volatile components such as low-molecular aldehydes and allyl alcohols. Polyurethane resins and polyurethane foams produced using these, There is a problem that an unpleasant odor is generated and a post-processing step is required to remove the odor. Although it is known that the use of a specific Lewis acid catalyst can reduce odor (see Patent Document 1), the effect of reducing odor is insufficient.

JP 2003-183383 A

  An object of this invention is to provide the manufacturing method of the polyoxyalkylene alcohol by which the post-process process which removes a low boiling-point volatile component is not required, and the odor was improved.

As a result of intensive studies, the present inventors have reached the present invention.
That is, the gist of the present invention is the following (I) and (II).
(I) The method for producing a polyoxyalkylene alcohol of the present invention comprises a by-product low-boiling compound having a boiling point of 150 ° C. or lower at a pressure of 0.1 MPa in the presence of a Lewis acid catalyst (a) in a reaction vessel (1) ( b) a step of addition-polymerizing the alkylene oxide (d) to the active hydrogen-containing compound (c) while continuously or intermittently removing it from the system, and (b) continuously or intermittently removed from the system. The gist is that the method is a method of continuously or intermittently removing the gas phase in the reaction vessel (1) during the addition polymerization.
(II) The method for producing a foamed or non-foamed polyurethane resin of the present invention is a method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component with an organic polyisocyanate (C), and at least a part of the polyol component. And using a polymer alcohol (B) obtained by polymerizing a vinyl monomer (f) in the polyoxyalkylene alcohol (A) and / or (A) obtained by the production method of (I) above. And

  According to the method for producing a polyoxyalkylene alcohol of the present invention, a post-treatment step for removing low-boiling volatile components is not required, production efficiency is improved, and odor generation can be reduced.

It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention. It is the schematic which shows an example of the embodiment of this invention.

In the production method of the present invention, the alkylene oxide (d) is addition-polymerized to the active hydrogen-containing compound (c) in the presence of the Lewis acid catalyst (a).
In the present invention, the Lewis acid catalyst (a) used at the time of addition of the alkylene oxide (d) is not particularly limited as long as it is an acidic catalyst for ring-opening addition polymerization of a cyclic ether, but preferably boron, aluminum, tin, antimony, An acidic catalyst containing at least one element (a1) selected from the group consisting of iron, phosphorus, zinc, titanium, zirconium and beryllium.
Examples of the acidic catalyst containing the element (a1) include a halide of the element (a1) and an alkylated and / or phenylated product (of the a1), and two or more kinds may be used in combination. Specific examples include the following.
(I) Halide of element (a1) Boron compounds such as boron trifluoride and boron trichloride; Aluminum compounds such as aluminum chloride and aluminum bromide; Tin compounds such as tin tetrafluoride and tin tetrachloride; Antimony fluoride And antimony compounds such as antimony chloride; iron compounds such as ferric chloride; phosphorus compounds such as phosphorus pentafluoride; zinc compounds such as zinc chloride; titanium compounds such as titanium tetrachloride; zirconium compounds such as zirconium chloride; (Ii) Alkylation and / or phenylation of element (a1) Triphenylboron, tri (t-butyl) boron, tris (pentafluorophenyl) boron, bis (pentafluorophenyl) -t- Butyl boron, bis (pentafluorophenyl) boron fluoride, di (t-butyl) Boron compounds, boron compounds such as (pentafluorophenyl) boron difluoride; triethylaluminum, triphenylaluminum, diphenyl-t-butylaluminum, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum Aluminum compounds such as bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) aluminum difluoride and (t-butyl) aluminum difluoride; zinc such as diethyl zinc Compounds; etc. Among these (i) and (ii), from the viewpoint of the reactivity during addition polymerization and the reactivity of the produced polyoxyalkylene alcohol, alkylation of boron trifluoride and element (a1) and / or Phenylates are preferred , More preferably boron trifluoride, tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum, particularly preferably tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum.

In the present invention, examples of the active hydrogen-containing compound (c) include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphoric acid compound.
Examples of the hydroxyl group-containing compound include alcohol and alkanolamine. Moreover, the compound (polyether alcohol) of the structure which the below-mentioned alkylene oxide (d) was added to the compound (alcohol, an amino group containing compound, carboxylic acid, phosphoric acid, etc.) which has active hydrogen is mentioned. Two or more of these may be used in combination. In addition, said polyether alcohol may be obtained using catalysts other than Lewis acid catalyst (a).

Examples of the alcohol include monohydric alcohols such as methanol, ethanol, butanol and octanol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, and 3-methylpentanediol. Dihydric alcohols such as diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene and 2,2-bis (4,4′-hydroxycyclohexyl) propane; Trivalent alcohols such as glycerin and trimethylolpropane; pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc. 4- to 8-valent alcohol; phenol such as phenol and cresol; polyhydric phenol such as pyrogallol, catechol and hydroquinone; bisphenol such as bisphenol A, bisphenol F and bisphenol S; polybutadiene alcohol; castor oil alcohol; hydroxyalkyl (meth) acrylate (Co) polymers and polyfunctional (2-100) alcohols such as polyvinyl alcohol, and the like, and those having 1 to 20 carbon atoms are preferred.
Examples of the polybutadiene alcohol 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. Among polybutadiene alcohols, polybutadiene glycol includes polybutadiene homopolymers and copolymers (such as styrene butadiene copolymers and acrylonitrile butadiene copolymers) and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%). It is.
Castor oil-based alcohols include castor oil and modified castor oil (such as 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 (butylamine and the like) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine and diethylenetriamine; piperazine, N-aminoethylpiperazine and the like. Other heterocyclic polyamines described in JP-B No. 55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenylamine Aromatic polyamines such as terdiamine and polyphenylmethane polyamine; polyamide polyamines [eg dicarboxylic acids (such as dimer acids) and excess (2 per mole of acid) Low molecular weight polyamide polyamines obtained by condensation with polyamines (such as the above-mentioned alkylene diamines and polyalkylene polyamines); polyether polyamines [hydrides of cyanoethylates of polyether alcohols (polyalkylene glycols, etc.)]; cyanoethylation Polyamines [for example, cyanoethylated polyamines obtained by addition reaction of acrylonitrile and polyamines (such as the above-mentioned alkylene diamines and polyalkylene polyamines). For example, biscyanoethyldiethylenetriamine and the like]; hydrazines (such as hydrazine and monoalkyl hydrazine), dihydrazides (such as succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and terephthalic acid dihydrazide), guanidines (such as butylguanidine and 1-cyanoguanidine) And dicyandiamide and the like; and a mixture of two or more thereof, and those having 1 to 20 carbon atoms are preferred.
Examples of amino alcohols include alkanolamines such as mono-, di- and tri-alkanolamines (monoethanolamine, monoisopropanolamine, monobutanolamine, triethanolamine and tripropanolamine); 1 to C4) Substituents [N, N-dialkylmonoalkanolamine (N, N-dimethylethanolamine, N, N-diethylethanolamine etc.) and N-alkyldialkanolamine (N-methyl) Diethanolamine and N-butyldiethanolamine etc.)]; and nitrogen atom quaternized products thereof 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 and 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, and 3-methylpentanedithiol.
Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  Of these active hydrogen-containing compounds (c), a hydroxyl group-containing compound is preferable, and a polyhydric alcohol and an alkylene oxide adduct of a polyhydric alcohol are more preferable.

The alkylene oxide (d) to be addition-polymerized to the active hydrogen-containing compound (c) is preferably C1 to C10, and includes EO, PO, 1,2-, 1,3-, 1,4- and 2,3- Examples include butylene oxide and styrene oxide. These two types may be used in combination. Of these, preferred are PO and / or EO, and more preferred is PO.
The number of moles of alkylene oxide (d) added to the active hydrogen-containing compound (c) is 0.5 to 300 with respect to 1 mole of active hydrogen from the viewpoint of easy removal of the by-product low-boiling compound (b). Mole is preferable, more preferably 0.7 to 150 mol, and particularly preferably 1 to 50 mol.
Examples of the method for adding (d) include, but are not limited to, single addition, random addition in the case of using two or more kinds of (d), and block addition.

The conditions for the addition polymerization of the alkylene oxide (d) may be a conventional method. From the viewpoint of the reactivity of the addition polymerization, the amount of the Lewis acid catalyst (a) used depends on the polyoxyalkylene alcohol (A) to be produced. On the other hand, it is preferably 0.00001 to 10%, more preferably 0.0001 to 1%, and the reaction temperature is preferably 0 to 250 ° C, more preferably 20 to 180 ° C.
In the above and the following, “%” means “% by weight” unless otherwise specified.

Specific examples of the by-product low-boiling compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa include formaldehyde (boiling point−19 ° C.), acetaldehyde (boiling point 20 ° C.), propionaldehyde (boiling point 48 ° C.), and allyl alcohol. And compounds having 0 to 2 moles of alkylene oxide (d) added thereto. These are volatile components and have an odor. These components are usually generated in an amount of 0.0001 to 10% with respect to the polyoxyalkylene alcohol (A).
Above and below, pressures are stated as absolute pressures unless otherwise noted.

In the production method of the present invention, in the step of addition polymerization of alkylene oxide (d) to active hydrogen-containing compound (c) in reaction vessel (1), a by-product low-boiling compound having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa. (B) is removed continuously or intermittently. As a method of removing out of the system, a method of removing the gas phase containing the by-product low boiling point compound (b) and the unreacted alkylene oxide (d) out of the system is taken.
The reaction vessel (1) may be any vessel that can be used for the addition reaction of alkylene oxide, but is preferably a vessel that can withstand a pressure of 1 MPa, can be heated and cooled, and is equipped with a stirring device. Examples of the material of the reaction tank (1) include glass, iron, stainless steel, aluminum, various alloys, carbon, and the like, and stainless steel having corrosion resistance is desirable.

  The temperature at which the gas phase is removed from the system may be a temperature at which the alkylene oxide (d) is subjected to addition polymerization, and is preferably 0 to 250 ° C, more preferably 20 to 180 ° C.

  The pressure for removing the gas phase out of the system is preferably 1 MPa or less from the viewpoint of the addition polymerization of alkylene oxide (d) and the ease of gas phase removal, and more aggressively the gas phase. In order to remove, it is more preferably 0.0001 to 0.1 MPa, and further preferably 0.001 to 0.08 MPa.

  In the present invention, the adsorption tower (2) used when the adsorbent (e) adsorbs and removes the by-product low-boiling compound (b) can be filled with the adsorbent, and the adsorbent is passed through the adsorption tower. There is no particular limitation as long as the container has a structure that does not diffuse out of the container, but it is desirable to have a temperature adjusting means (heating and cooling) and / or a pressure adjusting means (pressurizing and depressurizing), and the material is corrosion resistant. Stainless steel or the like with is desirable.

  In the present invention, by-product low boiling point compound (b) and alkylene oxide (d) (that is, adsorbed on unreacted alkylene oxide (d1) and / or adsorbent (e) described later, and then desorbed. The distillation column (3) used for separating the formed alkylene oxide (d3) is not particularly limited as long as it is a normal distillation column or rectification column used for refining petrochemicals, and its material is corrosion resistant. Stainless steel or glass with properties is desirable.

The present invention will be described based on a schematic diagram showing an example of the embodiment of the present invention shown in FIG.
During the step of adding the alkylene oxide (d) to the active hydrogen-containing compound (c) in the reaction tank (1) through the raw material supply line (4) and subjecting it to addition polymerization, a by-product low-boiling compound (b) and unreacted alkylene The gas phase containing oxide (d1) is removed continuously or intermittently from the removal line (5).

  In the embodiment of FIG. 1, intermittent gas phase removal includes charging alkylene oxide (d) in portions (preferably 2 to 100 times) and repeating the reaction and gas phase removal each time it is charged. . The temperature at which the gas phase is intermittently removed may be a temperature at which the alkylene oxide (d) is added. When the gas phase is intermittently removed, the reaction vessel (1) is pressurized (for example, 0.1 to 1.0 MPa) when (d) is reacted, and the gas phase is removed from the reaction vessel (1). Thus, the pressure can be reduced (for example, 0.001 to 0.08 MPa) alternately.

  In the embodiment of FIG. 1, continuous removal of the vapor phase out of the system means that the vapor phase is removed from the reaction vessel (1) at the same time as the alkylene oxide (d) is continuously charged. Continuous gas phase removal is performed with heating and / or reduced pressure. The temperature at which the gas phase is continuously removed may be a temperature at which the alkylene oxide (d) is added. The degree of reduced pressure is preferably 0.001 to 0.1 MPa, more preferably 0.01 to 0.08 MPa.

  In the embodiment of FIG. 1, by removing the gas phase from the reaction tank (1) with a vacuum pump or the like and removing it outside the system, the reaction tank (1) is depressurized and the gas phase in the reaction tank (1) is removed from the system. Can be removed.

A description will be given based on the schematic diagram showing an example of the embodiment of the present invention shown in FIG.
The reaction tank (1) and the adsorption tower (2) are removed during the addition polymerization of the alkylene oxide (d) through the raw material supply line (4) to the active hydrogen-containing compound (c) in the reaction tank (1). By linking with the line (5), the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) are adsorbed continuously or intermittently on the adsorbent (e) packed in the adsorption tower (2). To remove it from the system.

  In the embodiment of FIG. 2, intermittent gas phase removal means that alkylene oxide (d) is divided (preferably 2 to 100 times) and charged and reacted in the reaction vessel (1), and the gas phase is removed. It is sent to the adsorption tower (2) through the line (5), and the reaction tank (1) is unreacted with the by-product low-boiling compound (b) by heating or cooling and / or pressurizing or depressurizing as necessary. It means that the alkylene oxide (d1) is adsorbed on the adsorbent (e) packed in the adsorption tower (2) and removed out of the reaction system. The temperature at which the gas phase is intermittently removed from the reaction vessel (1) may be a temperature at which the alkylene oxide (d) is added to the active hydrogen-containing compound (c). The degree of reduced pressure is preferably 0.0001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

  In the embodiment of FIG. 2, the continuous gas phase removal means that the alkylene oxide (d) is reacted in the reaction vessel (1) and a part of the gas phase is removed through the removal line (5) in the adsorption tower (2). The reaction tank (1) is heated or cooled and / or pressurized or depressurized as necessary to remove the by-product low boiling point compound (b) and unreacted alkylene oxide (d1) by an adsorption tower ( It means that the adsorption to the adsorbent (e) filled in 2) and the removal from the reaction system are performed simultaneously. The temperature at which the gas phase is continuously removed may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of vacuum is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

In the embodiment of FIG. 2, when reducing the pressure, the reaction tank (1) is depressurized by sucking the gas phase from the reaction tank (1) with a vacuum pump or the like and removing it out of the system. ) Can be removed out of the system, but from the viewpoint of adsorption efficiency, it is preferable that the adsorption tower (2) is sucked with a pump or the like from a different end from the removal line (5) side to reduce the pressure. .
Further, the recovery line 1 (7) can be connected to an end portion different from the removal line (5) of the adsorption tower (2).

A description will be given based on the schematic diagram showing an example of the embodiment of the present invention shown in FIG.
The reaction tank (1) and the adsorption tower (2) are removed during the addition polymerization of the alkylene oxide (d) through the raw material supply line (4) to the active hydrogen-containing compound (c) in the reaction tank (1). By linking with the line (5), the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) are adsorbed continuously or intermittently on the adsorbent (e) packed in the adsorption tower (2). The alkylene oxide (d2) which has been removed by vapor phase and has not been adsorbed is returned to the reaction vessel (1) again continuously or intermittently through the circulation line (6). The flow rate when the gas phase is continuously circulated between the reaction tank (1) and the adsorption tower (2) is preferably 1/10000 to 100 times the capacity of the reaction tank (1) per minute, more preferably This is the rate at which 1/1000 to 50 times the volume is replaced.

  In the embodiment of FIG. 3, intermittent gas phase removal means that alkylene oxide (d) is divided (preferably 2 to 100 times) and charged and reacted in the reaction vessel (1), and the gas phase is removed. It is sent to the adsorption tower (2) through the line (5), and the reaction tank (1) is unreacted with the by-product low-boiling compound (b) by heating or cooling and / or pressurizing or depressurizing as necessary. The alkylene oxide (d1) was adsorbed on the adsorbent (e) packed in the adsorption tower (2), and the alkylene oxide (d2) not adsorbed on the adsorbent (e) was recycled to the reaction tank (1) ( 6) means repeated sending through. The temperature at which the gas phase is intermittently removed from the reaction vessel (1) may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of reduced pressure is preferably 0.0001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

  In the embodiment of FIG. 3, the continuous gas phase removal means that the alkylene oxide (d) is reacted in the reaction vessel (1) and a part of the gas phase is removed through the removal line (5) in the adsorption tower (2). (B) and unreacted alkylene oxide (d1) are packed in the adsorption tower (2) by heating or cooling the reaction tank (1) and / or pressurizing or depressurizing as necessary. This means that the alkylene oxide (d2) adsorbed by the adsorbent (e) and not adsorbed is simultaneously sent to the reaction vessel (1) through the circulation line (6). The temperature at which the gas phase is continuously removed may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of vacuum is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

A description will be given based on the schematic diagram showing an example of the embodiment of the present invention shown in FIG.
The reaction tank (1) and the adsorption tower (2) are removed during the addition polymerization of the alkylene oxide (d) through the raw material supply line (4) to the active hydrogen-containing compound (c) in the reaction tank (1). By linking with the line (5), the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) are continuously adsorbed to the adsorbent (e) packed in the adsorption tower (2). Remove outside. During the reaction and / or after completion of the reaction, the adsorption tower (2) and the reaction tank (1) are shut off by valves provided in the removal line (5) and the circulation line (6), and the adsorption tower (2) is heated and / or Alternatively, by reducing the pressure, alkylene oxide (d3) adsorbed on (b) and adsorbent (e) is desorbed from adsorbent (e). (B) and (d3) desorbed from the adsorbent (e) are sent to the first distillation column (31) through the recovery line 1 (7), and a compound having a higher boiling point than the alkylene oxide (d) is separated. The compounds other than the high boiling point compounds are further sent to the second distillation column (32) through the recovery line 2 (8) to separate the low boiling point compounds from the alkylene oxide (d), and then passed through the recovery line 3 (11). The recovered alkylene oxide (d4) is recovered in the recovery tank (12). The compound having a higher boiling point than (d) separated in the first distillation column (31) is discarded through a high boiling point compound extraction line (9). The compound having a lower boiling point than (d) separated in the second distillation column (32) is discarded through the low boiling point compound extraction line (10).

  In the embodiment of FIG. 4, intermittent gas phase removal means that alkylene oxide (d) is divided (preferably 2 to 100 times) and charged and reacted in the reaction vessel (1), and the gas phase is removed. It is sent to the adsorption tower (2) through the line (5), and the reaction tank (1) is unreacted with the by-product low-boiling compound (b) by heating or cooling and / or pressurizing or depressurizing as necessary. The alkylene oxide (d1) was adsorbed on the adsorbent (e) packed in the adsorption tower (2), and the alkylene oxide (d2) not adsorbed on the adsorbent (e) was recycled to the reaction tank (1) ( 6) means repeated sending through. The temperature at which the gas phase is intermittently removed from the reaction vessel (1) may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of reduced pressure is preferably 0.0001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

  In the embodiment of FIG. 4, continuous gas phase removal means that the alkylene oxide (d) is reacted in the reaction vessel (1), and a part of the gas phase is removed through the removal line (5) in the adsorption tower (2). (B) and unreacted alkylene oxide (d1) are packed in the adsorption tower (2) by heating or cooling the reaction tank (1) and / or pressurizing or depressurizing as necessary. This means that the adsorbent (e) adsorbed and the alkylene oxide (d2) not adsorbed are returned to the reaction tank (1) through the circulation line (6) at the same time. The temperature at which the gas phase is continuously removed may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of vacuum is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

A description will be given based on a schematic diagram showing an example of the embodiment of the present invention shown in FIG.
In the embodiment of the present invention shown in FIG. 5, in addition to the embodiment of the present invention shown in FIG. 4, the recovered alkylene oxide (d4) is transferred to the reaction vessel (1) through the recovery line 4 (13). Continuously or intermittently sent to carry out addition polymerization to the active hydrogen-containing compound (c).

A description will be given based on the schematic diagram showing an example of the embodiment of the present invention shown in FIG.
The reaction tank (1) and the distillation column (3) are removed during the addition polymerization of the alkylene oxide (d) through the raw material supply line (4) to the active hydrogen-containing compound (c) in the reaction tank (1). By connecting with the line (5), the by-product low-boiling point compound (b) and the unreacted alkylene oxide (d1) are continuously removed from the system by sending them to the distillation column (3). Unreacted alkylene oxide (d1) is sent to the first distillation column (31) through the removal line (5) to separate a compound having a higher boiling point than the alkylene oxide (d). The compounds other than the high boiling point compounds are further sent to the second distillation column (32) through the recovery line 2 (8) to separate the low boiling point compounds from the alkylene oxide (d), and then passed through the recovery line 3 (11). The recovered alkylene oxide (d4) is recovered in the recovery tank (12). The compound having a higher boiling point than (d) separated in the first distillation column (31) is discarded through a high boiling point compound extraction line (9). The compound having a lower boiling point than (d) separated in the second distillation column (32) is discarded through the low boiling point compound extraction line (10).

In the embodiment of FIG. 6, intermittent gas phase removal means that alkylene oxide (d) is divided (preferably 2 to 100 times) and charged and reacted in the reaction vessel (1), and the gas phase is removed. It means sending to the distillation column (31) through the line (5) and further sending to the distillation column (32) through the recovery line 2 (8), and recovering the recovered alkylene oxide (d4) to the recovery tank (12). To do.
The temperature of the reaction vessel (1) when intermittently removing the gas phase from the reaction vessel (1) may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of vacuum in the reaction tank (1) is preferably 0.0001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.
Continuous gas phase removal means that the alkylene oxide (d) is reacted in the reaction vessel (1), the gas phase is sent to the distillation column (31) through the removal line (5), and further the recovery line 2 (8). Means that the recovered alkylene oxide (d4) is recovered in the recovery tank (12) at the same time. The temperature of the reaction vessel (1) when continuously removing the gas phase may be a temperature at which (d) is added to the active hydrogen-containing compound (c). The degree of vacuum in the reaction tank (1) is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa.

A description will be given based on the schematic diagram showing an example of the embodiment of the present invention shown in FIG.
In the embodiment of the present invention shown in FIG. 7, in addition to the embodiment of the present invention shown in FIG. 6, the recovered alkylene oxide (d4) is transferred to the reaction vessel (1) through the recovery line 4 (13). Continuously or intermittently sent to carry out addition polymerization to the active hydrogen-containing compound (c).

  A method of sending a gas phase containing a by-product low-boiling-point compound (b) and unreacted alkylene oxide (d1) to the adsorption tower (2), and the non-adsorbed alkylene oxide (d2) from the adsorption tower (2) to the reaction tank Examples of the method of returning to (1) and the method of sending the adsorbed alkylene oxide (d3) to the distillation column (3) include a method using a pressure difference, and a vacuum pump or blower can be used. A method may be used.

  A method of charging alkylene oxide (d) into reaction tank (1), a method of sending recovered alkylene oxide (d4) to recovery tank (12), and a method of sending recovered alkylene oxide (d4) to reaction tank (1) Examples of the method include a method using a pressure difference, and a commonly used liquid phase pump can be used, but other methods may be used.

  As a method of returning the recovered alkylene oxide (d4) to the reaction tank (1), a method of directly returning to the reaction tank (1) through the recovery line 4 (13), or a return to the raw material supply line (4) through the recovery line 4 (13). There is a method of joining and returning to the reaction tank (1), but other methods may be used.

  The temperature at which the by-product low-boiling compound (b) and the unreacted alkylene oxide (d1) are adsorbed on the adsorbent (e) may be a temperature at which (d) is added to the active hydrogen-containing compound (c). -250 degreeC is preferable, More preferably, it is 20-180 degreeC, and you may heat an adsorption tower (2) as needed. The pressure may be a pressure for adding (d) to the active hydrogen-containing compound (c), and is preferably 0.001 to 0.5 MPa. Two or more adsorption towers (2) may be used as necessary, and each may be operated simultaneously or alternately.

  The temperature at which the by-product low-boiling compound (b) and the adsorbed alkylene oxide (d3) are desorbed from the adsorbent (e) may be a condition for reactivating the adsorbent (e), and is 0 to 400 ° C. Is preferable, more preferably 5 to 200 ° C, and still more preferably 10 to 150 ° C. The degree of reduced pressure is preferably 0.0001 to 0.1 MPa, more preferably 0.001 to 0.08 MPa, and still more preferably 0.001 to 0.05 MPa.

  Specifically, the adsorbent (e) filled in the adsorption tower (2) is at least one compound selected from the group consisting of silica gel, synthetic zeolite, activated clay, activated alumina, and activated carbon. Among these, a molecular sieve which is a synthetic zeolite is preferable from the viewpoint of adsorption and desorption efficiency. The use weight of (e) is preferably 1 to 3000 times, particularly preferably 10 to 2000 times, based on the generated weight of the by-product low-boiling compound (b).

  As the distillation column (3) {(31) and (32)}, known distillation can be used, and it is preferable to use a plate-type distillation column and a packed distillation column, and if necessary, combine two or more groups. May be used. Moreover, you may implement combining extractive distillation etc. as needed. When there are two or more distillation columns (3), only one of them may be used as necessary.

  The Lewis acid catalyst (a) may be neutralized, decomposed, removed or the like as necessary after completion of the addition polymerization.

  As a decomposition method, there is a method of adding water and / or an alcohol compound and, if necessary, a basic substance such as an alkali compound or an amine compound. As the alcohol compound, the aforementioned alcohol and / or phenol can be used. Examples of the alkali compound include alkali metal hydroxides (such as potassium hydroxide, sodium hydroxide, and cesium hydroxide), alkali metal alcoholates (such as potassium methylate and sodium methylate), and mixtures of two or more of these. Of these, alkali metal hydroxides are preferred from the viewpoint of decomposition efficiency. As the amine compound, one or more selected from the amino group-containing compounds described above can be used.

At the time of decomposition, from the viewpoint of decomposition efficiency, the temperature is preferably 10 ° C to 180 ° C, more preferably 80 to 150 ° C. The decomposition may be performed in a sealed state, may be performed while being exhausted by connecting to a vacuum source, or may be performed while continuously adding water or an alcohol compound. The water or alcohol compound to be added may be added in a liquid state, or may be added in a vapor or solid state. The amount of water and alcohol compound used is preferably from 0.1 to 100%, more preferably from 1 to 20%, based on the addition product. The amount of caustic alkali or amine compound used is preferably from 0.1 to 10%, more preferably from 0.3 to 2%, based on the addition product.
As a removing method, any known method may be used. For example, hydrotalcite-based adsorbents (KYOWARD 500, KYOWARD 1000, KYOWARD 2000, etc. (all manufactured by Kyowa Chemical Industry Co., Ltd.)) and filter aids such as diatomaceous earth (Radiolite 600, Radiolite 800, and Radiolite 900) Etc. (both manufactured by Showa Chemical Industry Co., Ltd.)). 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, and meta-aramid are exemplified, and 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.

  The adsorbent may be removed as necessary. The removal method may be carried out by any generally known method, and examples thereof include filtration using the above-mentioned adsorbent and filter aid.

  When the water content is high, the water may be subsequently dehydrated at 90 to 160 ° C. under reduced pressure (0.01 MPa or less). As a method, a batch method or a shower ring method may be used.

  In any step, it is preferably performed in the absence of oxygen, and the oxygen concentration is preferably 1000 ppm or less, and more preferably 500 ppm or less. If it is 1000 ppm or less, the ether bond of the polyoxyalkylene alcohol is hardly oxidized, and as a result, it is difficult to be colored. The reduction of the oxygen concentration can be carried out by passing an inert gas such as nitrogen gas or argon gas into the filtration device, which is preferable.

The polyoxyalkylene alcohol obtained by the production method of the present invention (especially a polyoxyalkylene polyol having 2 to 8 or more valences) can be used for various applications, but for producing a foamed or non-foamed polyurethane resin. Preferably used.
That is, when producing a foamed or non-foamed polyurethane resin by reacting a polyol component and an organic polyisocyanate (C) in the presence of an additive as necessary, as a part of the polyol component, a polyoxyalkylene alcohol (A ) And / or (A), the polymer alcohol (B) obtained by polymerizing the vinyl monomer (m) can be used.

  The polymer alcohol (B) can be produced by polymerizing a vinyl monomer in the polyoxyalkylene alcohol (A) (preferably a polyoxyalkylene polyol) by an ordinary method. For example, in (A), a vinyl monomer is polymerized in the presence of a radical polymerization initiator, and the resulting polymer is stably dispersed. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351 and Japanese Examined Patent Publication No. 39-25737.

  As the organic polyisocyanate (C), those conventionally used for polyurethane production can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

  In the polyurethane production method of the present invention, if necessary, foaming agents, foam stabilizers, urethanization catalysts, colorants (dyes, pigments), plasticizers, organic fillers, flame retardants, anti-aging agents, antioxidants and the like are known. Can be reacted in the presence of these additives.

  The isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in the polyurethane production method of the present invention is preferably 80 to 150, more preferably 85 to 135, and particularly preferably 90. ~ 130.

Moreover, the conditions which make a polyol component and organic polyisocyanate (C) react may be the well-known conditions normally used.
As an example, first, a predetermined amount of a polyol component and, if necessary, an additive are mixed. The mixture and polyisocyanate are then rapidly mixed using a polyurethane low pressure or high pressure injection foaming machine or a stirrer. The obtained liquid mixture is poured into a closed mold or an open mold (made of metal or resin) to cause urethanization reaction, and after curing for a predetermined time, it is demolded to obtain a polyurethane resin.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.

The evaluation standards for odor are as follows.
4 points: Almost no odor 3 points: Slight odor 2 points: Slightly unpleasant odor.
1 point: There is an unpleasant odor.

<Example 1>
As shown in FIG. 1, the removal line (5) was connected to a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, and a raw material supply line (4). A diaphragm type vacuum pump was installed at the end of the removal line (5) (end not connected to the reaction vessel (1)).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, PO was controlled from the raw material supply line (4) so that the reaction temperature was maintained at 50 to 60 ° C. While throwing. However, PO was charged 20 times, and once PO was charged, 150 g of PO was charged in 10 minutes, and then reduced in pressure (0.01 MPa) by a diaphragm vacuum pump installed in the removal line (5). The step of distilling off volatile components having a low boiling point for 15 minutes was repeated 20 times. PO was added until the amount in the autoclave reached 2000 ml, and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-1). The hydroxyl value was 56.0, the odor evaluation was 3, and the reaction time was 13.3 hours in total (from the start of PO addition to the end of aging).

<Example 2>
In Example 1, it implemented similarly to Example 1 except having set 400 g of glycerin PO adduct (hydroxyl value 280) to 200 g, and obtained the liquid glycerin PO adduct (A-2). The hydroxyl value was 28.1, the odor evaluation was 3, and the reaction time was 15.0 hours in total.

<Example 3>
In Example 1, PO is charged in 20 portions (PO is charged once for 10 minutes, and then reduced in pressure (0.01 MPa) by a diaphragm type vacuum pump installed in the removal line (5)). Instead of repeating the process 20 times), the PO is continuously charged over 4 hours from the raw material supply line (4), and the removal line (5 ) Under reduced pressure (0.01 MPa), except that the volatile component was distilled off at the same time to obtain a liquid glycerin PO adduct (A-3). The hydroxyl value was 56.0, the odor evaluation was 4, and the total reaction time was 9.0 hours.

<Example 4>
In Example 3, it implemented like Example 3 except having changed 400 g of PO addition products (hydroxyl value 280) of glycerin to 200 g, and obtained liquid glycerin PO addition product (A-4). The hydroxyl value was 28.0, the odor evaluation was 4, and the reaction time was 11.0 hours in total.

<Example 5>
As shown in FIG. 2, a 2500 ml stirring device, a temperature control device, a stainless steel autoclave as a reaction tank (1) with a raw material supply line (4), and an external heater filled with 1000 g of molecular sieve 4A are attached. The adsorption tower (2) was connected by a removal line (5). Further, the recovery line 1 (7) was connected to the adsorption tower (2) at an end other than the end of the adsorption tower (2) connected to the removal line (5). A diaphragm type vacuum pump was installed in the removal line (5) and the recovery line 1 (7).
405 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane were charged. Gas phase containing by-product low-boiling compounds by continuously feeding PO through the raw material supply line (4) while controlling the reaction temperature so as to maintain 50 to 60 ° C. over 4 hours, and using a diaphragm type vacuum pump. Was continuously removed from the autoclave, the by-product low-boiling compounds were adsorbed on the molecular sieve, and the gas not adsorbed was discarded through the recovery line 1. The adsorption tower (2) was operated at a temperature of 40 ° C. and a pressure of 0.1 MPa. When the amount of liquid in the autoclave reached 2025 ml, the charging was stopped and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-5). The hydroxyl value was 56.1, the odor evaluation was 3, and the total reaction time was 9.0 hours.

<Example 6>
As in the embodiment shown in FIG. 3, a 2500 ml stirrer, a temperature controller, a stainless steel autoclave as a reaction tank (1) with a raw material supply line (4), and an external heater filled with 1000 g of molecular sieve 4A are attached. The adsorption tower (2) was connected in the order of reaction tank (1) → removal line (5) → adsorption tower (2) → circulation line (6) → reaction tank (1). A diaphragm type vacuum pump was installed in the removal line (5) and the circulation line (6).
405 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane were charged. PO is continuously fed through the raw material supply line (4) while controlling the reaction temperature so that the reaction temperature is maintained at 50 to 60 ° C. over 4 hours, and the gas phase of the autoclave is flowed at 10 L / min using a diaphragm pump. Then, the reaction tank (1), the removal line (5), the adsorption tower (2), the circulation line (6), and the reaction tank (1) were simultaneously circulated. The adsorption tower (2) was operated at a temperature of 40 ° C. and a pressure of 0.1 MPa. When the amount of liquid in the autoclave reached 2025 ml, the charging was stopped and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-6). The hydroxyl value was 56.1, the odor evaluation was 3, and the total reaction time was 9.0 hours.

<Example 7>
As shown in FIG. 4, a 2500 ml stirring device, a temperature control device, a stainless steel autoclave as a reaction tank (1) with a raw material supply line (4), and an external heater filled with 500 g of molecular sieve 4A are attached. The adsorption tower (2) was connected in the order of reaction tank (1) → removal line (5) → adsorption tower (2) → circulation line (6) → reaction tank (1). Further, a distillation column (31) for removing by-product low molecular compounds having a higher boiling point than PO is connected to the adsorption tower (2) through a recovery line 1 (7), and further, a by-product low molecular compound having a lower boiling point than PO. A distillation column (32) for removing was connected through recovery line 2 (8). The distillation tower (32) and the stainless steel recovery tank (12) were connected through the recovery line 3 (11). A diaphragm type vacuum pump was installed in the removal line (5) and the recovery line 1 (7).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, the pressure in the autoclave, the adsorption tower (2) and the removal line (5) was reduced to 0.005 MPa. . The PO was continuously added through the raw material supply line (4) until the amount of liquid in the autoclave reached 2000 ml while controlling the PO so that the reaction temperature was maintained at 50 to 60 ° C. over 5 hours. After pouring PO, the mixture was aged at 70 ° C. for 5 hours. The adsorption tower (2) was controlled to 25 ° C. A liquid glycerin PO adduct (A-7) was obtained. The hydroxyl value was 55.9, the odor evaluation was 4, and the reaction time was 10 hours in total.
After completion of the reaction, the adsorption tower (2) is shut off from the autoclave, the by-product low-boiling compounds (b) and PO adsorbed at 100 ° C. and a reduced pressure of 0.005 MPa are desorbed from the molecular sieve, and the recovery line 1 ( 7) to the distillation column (31), by-product low molecular compounds having a higher boiling point than PO are removed from the high boiling point compound extraction line (9), and further to the distillation column (32) through the recovery line 2 (8), By-product low-molecular compounds having a lower boiling point than PO were removed from the low-boiling compound extraction line (10), and the distilled PO was recovered in the recovery tank (12) through the recovery line 3 (11).

<Example 8>
As in the embodiment shown in FIG. 5, a 2500 ml stirrer, a temperature controller, a stainless steel autoclave as a reaction tank (1) with a raw material supply line (4), and an external heater filled with 500 g of molecular sieve 4A are attached. The two adsorption towers (21) and (22) were connected as an adsorption tower (2) in parallel through a removal line (5) and a recovery line 1 (7). It connected in order of reaction tank (1)-> removal line (5)-> adsorption tower (2)-> circulation line (6)-> reaction tank (1). A diaphragm type vacuum pump was installed in the removal line (5). Further, the adsorption towers (21) and (22) are connected with a distillation tower (31) for removing by-product low molecular compounds having a boiling point higher than that of PO through a recovery line 1 (7), and further having a boiling point lower than that of PO. A distillation column (32) for removing byproduct low molecular weight compounds was connected through recovery line 2 (8). The distillation tower (32) and the stainless steel recovery tank (12) were connected through the recovery line 3 (11). The collection tank (12) and the raw material supply line (4) were connected through the collection line 4 (13).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, the pressure in the autoclave, the adsorption tower (21) and the removal line (5) was reduced to 0.005 MPa. . While continuously feeding PO through the raw material supply line (4) while maintaining the reaction temperature at 50 to 60 ° C., the gas phase in the reaction tank (1) is flowed at a flow rate of 10 L / min using a diaphragm pump. The reaction tank (1), the removal line (5), the adsorption tower (21), the recovery line 1 (6), and the reaction tank (1) were circulated in this order. The adsorption tower (2) was controlled to 25 ° C. Each time 400 g of PO was added, the adsorption towers (21) and (22) were used alternately. In addition, the unused adsorption tower is shut off from the reaction tank (1), and the by-product low-boiling compound (b) and PO adsorbed at 100 ° C. and a reduced pressure of 0.005 MPa are desorbed from the molecular sieve, It is sent to the distillation column (31) through the recovery line 1 (7) to remove high-boiling by-product low-molecular compounds from the high-boiling compound extraction line (9), and further to the distillation column (32) through the recovery line 2 (8). The low-boiling by-product low-molecular compound was removed from the low-boiling compound extraction line (10), and the distilled PO was recovered in the recovery tank (12) through the recovery line 3 (11). The recovered PO was returned to the reaction tank (1) through the recovery line 4 (13) and the raw material supply line (4).
PO was added until the liquid volume in the autoclave reached 2000 ml, and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-8). The hydroxyl value was 56.0, the odor evaluation was 4, and the reaction time was 10 hours in total.

<Example 9>
In Example 8, except performing 400 g of glycerin PO adduct (hydroxyl value 280) as 200 g, it carried out like Example 8 and obtained liquid glycerin PO adduct (A-9). The hydroxyl value was 27.9, the odor evaluation was 4, and the reaction time was 12.0 hours in total.

<Example 10>
As shown in FIG. 6, a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, a raw material supply line (4), and a by-product low-molecular compound having a boiling point higher than PO. A distillation column (31) for removal was connected through a removal line (5), and a distillation column (32) for removing a by-product low-molecular compound having a boiling point lower than that of PO was connected through a recovery line 2 (8). The distillation tower (32) and the stainless steel recovery tank (12) were connected through the recovery line 3 (11). A diaphragm type vacuum pump was installed in the removal line (5).
After charging 400 g of a glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, the pressure in the autoclave was reduced to 0.005 MPa. The PO is continuously fed through the raw material supply line (4) while controlling the reaction temperature so that the reaction temperature is maintained at 50 to 60 ° C., and the gas phase of the autoclave is flowed at a flow rate of 10 L / min using a diaphragm pump. (1) is sent to the distillation column (31) through the recovery line 1 (7) to remove high-boiling by-product low-molecular compounds from the high-boiling compound extraction line (9), and further through the recovery line 2 (8) to the distillation column. (32), the low-boiling by-product low-molecular compounds are removed from the low-boiling compound extraction line (10), and the distilled PO is recovered in the recovery tank (12) through the recovery line 3 (11). did.
PO was added until the liquid volume in the autoclave reached 2000 ml, and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-10). The hydroxyl value was 56.1, the odor evaluation was 4, and the reaction time was 12 hours in total.

<Example 11>
As in the embodiment shown in FIG. 7, a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, a raw material supply line (4), and a by-product low molecular compound having a boiling point higher than PO. A distillation column (31) for removal was connected through a removal line (5), and a distillation column (32) for removing a by-product low-molecular compound having a boiling point lower than that of PO was connected through a recovery line 2 (8). The distillation tower (32) and the stainless steel recovery tank (12) were connected through the recovery line 3 (11). A diaphragm type vacuum pump was installed in the removal line (5). The collection tank (12) and the raw material supply line (4) were connected through the collection line 4 (13).
After charging 400 g of a glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, the pressure in the autoclave was reduced to 0.005 MPa. The PO is continuously fed through the raw material supply line (4) while controlling the reaction temperature so that the reaction temperature is maintained at 50 to 60 ° C., and the gas phase of the autoclave is flowed at a flow rate of 10 L / min using a diaphragm pump. (1) is sent to the distillation column (31) through the recovery line 1 (7) to remove high-boiling by-product low-molecular compounds from the high-boiling compound extraction line (9), and further through the recovery line 2 (8) to the distillation column. (32), the low-boiling by-product low-molecular compounds are removed from the low-boiling compound extraction line (10), and the PO distilled through the recovery line 3 (11) is recovered in the recovery tank (12); The returned PO was simultaneously returned to the reaction vessel (1) through the recovery line 4 (13) and the raw material supply line (4). PO was added until the liquid volume in the autoclave reached 2000 ml, and then aged at 70 ° C. for 5 hours to obtain a liquid glycerin PO adduct (A-11). The hydroxyl value was 56.1, the odor evaluation was 4, and the reaction time was 12 hours in total.

<Example 12>
In Example 11, except performing 400 g of glycerin PO adduct (hydroxyl value 280) as 200 g, it carried out like Example 11 and obtained liquid glycerin PO adduct (A-12). The hydroxyl value was 28.1, the odor evaluation was 4, and the reaction time was 15.0 hours in total.

<Comparative Example 1>
As shown in FIG. 1, a stainless steel autoclave with a 2500 ml stirring device, a temperature control device, a raw material supply line (4), and a removal line (5) is charged with 400 g of a glycerin PO adduct (hydroxyl value 280). Tris (pentafluorophenyl) borane (0.09 g) was charged. PO is continuously added from the raw material supply line (4) until the amount of liquid in the autoclave reaches 2050 ml while controlling the reaction temperature to be kept at 50 to 60 ° C., and further aged at 70 ° C. for 5 hours. A glycerin PO adduct (B-1) was obtained. The hydroxyl value was 56.1, the odor evaluation was 1, and the total reaction time was 9 hours.

<Comparative example 2>
As shown in FIG. 1, a stainless steel autoclave with a 2500 ml stirring device, a temperature control device, a raw material supply line (4), and a removal line (5) is charged with 400 g of a glycerin PO adduct (hydroxyl value 280). After charging 0.09 g of tris (pentafluorophenyl) borane, PO is continuously controlled while maintaining the reaction temperature at 50 to 60 ° C. until the amount of liquid in the autoclave reaches 2050 ml from the raw material supply line (4). I put it in. PO was charged over 4 hours. Thereafter, it was further aged at 70 ° C. for 5 hours. After adding 200 ml of water, the low-boiling by-product was distilled off at atmospheric pressure through the removal line (5) while controlling at 105 to 110 ° C., and then the temperature was raised to 130 ° C. for 3 hours and the pressure was kept at 50 torr or less. And dehydrated to obtain a liquid glycerin PO adduct (B-2). The hydroxyl value was 55.9, the odor evaluation was 3, and the reaction time was 16 hours in total.

<Comparative Example 3>
In Comparative Example 1, a liquid glycerin PO adduct (B-3) was obtained in the same manner as in Comparative Example 1 except that 400 g of the glycerin PO adduct (hydroxyl value 280) was changed to 200 g. The hydroxyl value was 28.5, the odor evaluation was 1, and the reaction time was 11.0 hours in total.

<Comparative example 4>
In Comparative Example 2, a liquid glycerin PO adduct (B-4) was obtained in the same manner as in Comparative Example 2 except that 400 g of the glycerin PO adduct (hydroxyl value 280) was changed to 200 g. The hydroxyl value was 28.1, the odor evaluation was 3, and the reaction time was 18.0 hours in total.

The examples of the present invention are superior to Comparative Examples 1 and 3 with less odor. The reaction time is equivalent and the production efficiency is equivalent. In particular, Examples 3, 4 and 7 to 12 are excellent in terms of odor.
Moreover, the Example of this invention is equivalent or more in the point of an odor compared with Comparative Examples 2 and 4, and in Examples 3, 4, and 7-12, it is excellent in the point of an odor. And since the Example of this invention does not require a post-processing process, reaction time is short and it is very excellent at the point of production efficiency.
That is, it turns out that the Example of this invention is the manufacturing method which was excellent compared with the comparative example, and at least any one of an odor and production efficiency is equivalent or more.

  According to the method for producing a polyoxyalkylene alcohol of the present invention, a post-treatment step for removing a low boiling point volatile component is not required, the production efficiency is improved, and the odor of alcohol is improved. The obtained polyoxyalkylene alcohol is particularly useful as a raw material for a polyurethane resin (including polyurethane foam) obtained by reacting with a polyisocyanate.

1 Reaction tank 2 Adsorption tower 31 Distillation tower 1
32 Distillation tower 2
4 Raw material supply line 5 Removal line 6 Circulation line 7 Collection line 1
8 Collection line 2
9 High boiling point compound extraction line 10 Low boiling point compound extraction line 11 Recovery line 3
12 Collection tank 13 Collection line 4

Claims (9)

  In the reaction vessel (1), in the presence of the Lewis acid catalyst (a), the by-product low boiling point compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa is continuously or intermittently removed from the system, A step of addition polymerization of the alkylene oxide (d) to the active hydrogen-containing compound (c), wherein the method of continuously or intermittently removing (b) from the system is a gas phase in the reaction vessel (1) during the addition polymerization. A process for producing polyoxyalkylene alcohol (A), which is a method for continuously or intermittently removing sucrose from the system.   The method of continuously or intermittently removing the gas phase of the reaction vessel (1) from the system includes the by-product low-boiling compound (b) and the unreacted alkylene oxide (d1) gas phase of the reaction vessel (1). The method according to claim 1, wherein the adsorbent (e) filled in the adsorption tower (2) is adsorbed with (b) and (d) continuously or intermittently to the adsorption tower (2). Production method.   The production method according to claim 2, wherein the adsorbent (e) is at least one compound selected from the group consisting of silica gel, synthetic zeolite, activated clay, activated alumina, and activated carbon.   The production method according to claim 2 or 3, wherein the alkylene oxide (d2) not adsorbed by the adsorbent (e) is continuously or intermittently sent to the reaction vessel (1).   The adsorption tower (2) packed with the adsorbent (e) adsorbing the alkylene oxide (d3) adsorbed on the adsorbent (e) and the by-product low boiling point compound (b) is heated and / or reduced in pressure. (B) and (d3) are desorbed from (e), the desorbed (b) and (d3) are separated by a distillation column (3), and the separated (d3) is recovered as alkylene oxide (d4). The manufacturing method in any one of Claims 2-4 collect | recovered.   The production method according to claim 5, wherein the recovered alkylene oxide (d4) is continuously or intermittently sent to the reaction vessel (1).   The method of continuously or intermittently removing the gas phase of the reaction vessel (1) from the system is to remove the gas phase of the reaction vessel (1) containing the by-product low-boiling compound (b) and the unreacted alkylene oxide (d1). The production method according to claim 1, wherein the process is continuously or intermittently sent to the distillation column (3), (b) and (d1) are separated, and the separated (d1) is recovered as recovered alkylene oxide (d4).   The production method according to claim 7, wherein the recovered alkylene oxide (d4) is continuously or intermittently sent to the reaction vessel (1).   In a method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and an organic polyisocyanate (C), it is obtained by the production method according to any one of claims 1 to 8 as at least a part of the polyol component. A method for producing a foamed or non-foamed polyurethane resin using a polymer alcohol (B) obtained by polymerizing a vinyl monomer in the obtained polyoxyalkylene alcohol (A) and / or (A).