JP2015196648A - Production method of alkylene oxide addition product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an alkylene oxide addition product, with which a volatile component with a low boiling point is easily evaporated and removed and an unreacted alkylene oxide is easily separated, recovered and reused.SOLUTION: A production method of an alkylene oxide addition product includes a step of sending a reaction mixture (e) obtained by adding an alkylene oxide (d) to an active hydrogen-containing compound (c) in the presence of a Lewis acid catalyst (a) from a reactor to the outside of the system, and separating an unreacted alkylene oxide (d1) and a byproduct compound (b) with a low boiling point of 150°C or lower at pressure of 0.1 MPa from the reaction mixture (e), in which the content of the unreacted alkylene oxide (d1) in the reaction mixture (e) is 0.5 to 10 wt.% based on the weight of (e).

Description

  The present invention relates to a method for producing an alkylene oxide adduct.

  Usually, an alkylene oxide adduct is prepared by using an alkali metal such as potassium hydroxide or a Lewis acid such as aluminum chloride or boron trifluoride as a catalyst, and an active hydrogen-containing compound such as 1,2-propylene oxide or ethylene oxide. Obtained by addition polymerization of oxide.

  In particular, in polyoxyalkylene alcohols produced using a Lewis acid catalyst, alcohol derived from by-product low-boiling substances is generated, and the number-average functional group number decreases. A polyurethane resin or polyurethane foam produced using an alkylene oxide adduct having a reduced number-average functional group has a problem that physical properties such as strength are lowered. The odor can be reduced by addition-polymerizing an alkylene oxide to an active hydrogen-containing compound while continuously or intermittently devolatilizing the by-product low-boiling compound (b) in the presence of a Lewis acid catalyst. It is known that the decrease in the average number of functional groups can be suppressed (see Patent Document 1), but in this method, it takes a very long time to devolatilize the by-product low-boiling compound (b), and both are devolatilized together. Separation from unreacted alkylene oxide is difficult, and the amount of recovered unreacted alkylene oxide cannot be increased within the production time, and it is necessary to spend more time for rectification, resulting in an increase in cost due to the delay in production time. It was.

JP 2011-195836 A

  An object of the present invention is to provide a method for producing an alkylene oxide adduct that can easily devolatilize a volatile component having a low boiling point, and can easily separate and recover unreacted alkylene oxide and reuse it. .

As a result of intensive studies, the present inventor has reached the present invention.
That is, in the present invention, the reaction mixture (e) obtained by adding the alkylene oxide (d) to the active hydrogen-containing compound (c) in the presence of the Lewis acid catalyst (a) is sent out of the system from the reactor. A step of separating unreacted alkylene oxide (d1) and by-product low-boiling compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa from (e), and comprising unreacted alkylene oxide in the reaction mixture (e) It is a manufacturing method of the alkylene oxide adduct whose content of (d1) is 0.5 to 10 weight% on the basis of the weight of (e).

  According to the method for producing an alkylene oxide adduct of the present invention, a volatile component having a low boiling point can be easily devolatilized, and unreacted alkylene oxide can be easily separated and recovered and reused.

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 boron, aluminum, tin, antimony, iron, An acidic catalyst containing at least one element (a1) selected from the group consisting of phosphorus, zinc, titanium, zirconium and beryllium is preferred.
Examples of the acidic catalyst containing the element (a1) include a halide of the element (a1) and an alkylation and / or phenylation of the element (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), boron trifluoride is used from the viewpoints of reactivity during addition polymerization, reactivity of the produced alkylene oxide adduct and reduction of by-product unsaturated group-containing substances. And alkylation of element (a1) and Alternatively, phenylated compounds are preferable, more preferably boron trifluoride, tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum, particularly preferably tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum. .

  The unsaturated group-containing product as a by-product includes an unsaturated hydroxyl group-containing product, an unsaturated group-containing product formed by a transfer reaction of the raw material alkylene oxide, and a compound in which an alkylene oxide is added thereto. . For example, when the alkylene oxide is 1,2-propylene oxide, by-product allyl alcohol and an alkylene oxide adduct of allyl alcohol can be mentioned.

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 (alkylene oxide adduct) 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. The alkylene oxide adduct used as the hydroxyl group-containing compound may be obtained using a catalyst other than the 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 (hereinafter abbreviated as C) 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: 20 to 100%, for example). 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 cyanoethylated polyether alcohols (polyalkylene glycols, etc.)]; Polyamines [for example, cyanoethylated polyamines obtained by addition reaction of acrylonitrile and polyamines (such as the above-mentioned alkylene diamine and polyalkylene polyamine). 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 of these, and those of C1-20 are preferred.
As aminoalcohols, alkanolamines such as mono-, di- and tri-alkanolamines (monoethanolamine, monoisopropanolamine, monobutanolamine, triethanolamine and tripropanolamine etc.); these alkyls (C1 to C4) Substituents [N, N-dialkylmonoalkanolamine (N, N-dimethylethanolamine and N, N-diethylethanolamine etc.) and N-alkyldialkanolamine (N-methyldiethanolamine and N-butyldiethanolamine etc.)]; And a quaternized nitrogen atom by a quaternizing agent such as dimethyl sulfate or benzyl chloride, and those having C1 to 20 are preferable.

Examples of the carboxyl group-containing compound include C1-20 carboxylic acids; aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; and aliphatic polycarboxylic acids such as succinic acid and adipic acid. Acid; aromatic polycarboxylic acid such as phthalic acid, terephthalic acid and trimellitic acid; polycarboxylic acid polymer (functional group 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 subjected to addition polymerization to the active hydrogen-containing compound (c) is preferably C2 to C10, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO). 1), 1,2-, 1,3-, 1,4- and 2,3-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 is based on the weight of the alkylene oxide adduct to be produced. Is preferably 0.00001 to 10% by weight, more preferably 0.0001 to 1% by weight, and the reaction temperature is preferably 0 to 250 ° C., more preferably 20 to 180 ° C.

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 15% by weight based on the alkylene oxide adduct (A).
Above and below, pressures are stated as absolute pressures unless otherwise noted.

The production method of the present invention includes the following steps.
In the presence of the Lewis acid catalyst (a), the reaction mixture (e) obtained by adding the alkylene oxide (d) to the active hydrogen-containing compound (c) is sent out of the reactor, and unreacted alkylene oxide (d1 And a by-product low-boiling compound (b) having a boiling point of 150 ° C. or lower at a pressure of 0.1 MPa.

  The reaction mixture (e) is a mixture comprising the active hydrogen compound (c), the alkylene oxide (d), the Lewis acid catalyst (a), the produced alkylene oxide adduct, the by-product low boiling point compound (b) and the like. . When the step of removing unreacted alkylene oxide (d1) and (b) is performed at a temperature and pressure at which the reaction mixture (e) becomes a liquid phase, the reaction mixture (e) becomes a mixture consisting of a liquid phase, and the reaction mixture When the step of removing (d1) and (b) is performed at a temperature and pressure at which part of (e) becomes a gas phase, the reaction mixture (e) becomes a mixture consisting of a liquid phase and a gas phase.

  Examples of the method for separating (b) from the reaction mixture (e) include a method for separating the by-product low-boiling compound (b) by distillation.

The reactor used when adding the alkylene oxide (d) to the active hydrogen-containing compound (c) may be any vessel that can be used for the addition reaction of alkylene oxide, but from the viewpoint of production efficiency, a tubular reaction is used. A tubular reactor is preferred, which can withstand a pressure of 1 MPa, can be heated and cooled, and is equipped with a stirring device. A tubular reactor is a type of reactor that reacts while flowing fluid from one side to the other.
Examples of the material for the reactor include glass, iron, stainless steel, aluminum, various alloys, and carbon. Stainless steel having corrosion resistance is desirable.

  The temperature at which (d1) and (b) are separated from the reaction mixture (e) by a devolatilizer outside the reactor system is preferably 0 to 250 ° C, more preferably 20 to 180 ° C.

  The pressure when separating (d1) and (b) from the reaction mixture (e) with a devolatilizer is preferably 1 MPa or less from the viewpoint of ease of vapor phase removal, and more aggressively remove the gas phase. Therefore, it is more preferably 0.0001 to 0.1 MPa, and further preferably 0.001 to 0.08 MPa.

When separating (d1) and (b) from the reaction mixture (e) with a devolatilizer, in order to perform separation more efficiently, the content of unreacted alkylene oxide (d1) is the weight of (e). It should be 0.5 to 10% by weight as a reference, and preferably 1 to 10% by weight.
Examples of the method for adjusting the content of (d1) to the above range include a method for increasing or decreasing the amount of the Lewis acid catalyst (a) used.

For the same reason, the weight ratio [(b) / (d1)] between the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) in the reaction mixture (e) is 1/1 to 1 / 10 is desirable.
As a method of adjusting the weight ratio of (b) and (d1) to the above range, for example, a method of increasing or decreasing the amount of the Lewis acid catalyst (a) used can be mentioned.

  In the present invention, a distillation column can be used when separating the by-product low-boiling compound (b) by distillation, and the distillation column is a normal distillation column or rectification column used for refining petrochemicals. If it is, there will be no restriction | limiting in particular, As for the material, stainless steel, glass, etc. with corrosion resistance are desirable.

In the production method of the present invention, the average content of the by-product low-boiling compound (b) in the reaction mixture (e) is (e ) Is preferably 5% by weight or less, more preferably 2% by weight or less, and still more preferably 1% by weight or less.
In addition, content of (b) can be measured with normal measuring methods, such as a gas chromatography.
In the above and below, the average content of the by-product low-boiling compound (b) indicates the average content per unit time unless otherwise specified.

The present invention will be described based on a schematic diagram showing an example of the embodiment of the present invention shown in FIG.
In the embodiment shown in FIG. 1, during the step of addition polymerization of the active hydrogen-containing compound (c) and the alkylene oxide (d) through the raw material supply line (4) to the tubular reactor (1), the by-product is reduced. Boiling compound (b) and unreacted alkylene oxide (d1) are continuously removed from removal line (5).
First, during the reaction, the reaction mixture (e) is continuously sent from the tubular reactor (1) to the devolatilizer (2) through the feed line (6), and heated and / or decompressed as necessary. The by-product low boiling point compound (b) and unreacted alkylene oxide (d1) are volatilized and sent to the distillation column (3) through the gas phase removal line (5). The alkylene oxide (d) and the by-product low boiling point compound (b) are separated in the distillation column (3), and the alkylene oxide (d) is recovered in the recovery tank (9) through the tower top line (8). The recovered alkylene oxide (d) may be returned to the reactor (1) again through the recovered liquid feeding line (10). Further, the byproduct low boiling point compound (b) is discarded through the byproduct low boiling point compound extraction line (11). After removing the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) from the reaction mixture (e), the alkylene oxide adduct is withdrawn from the recovery line (7). The alkylene oxide adduct extracted from the recovery line (7) may be subjected to addition polymerization again.

In the embodiment of FIG. 1, the recovered alkylene oxide (d) is returned to the reactor (1) again by using a liquid feed pump, utilizing a pressure difference, utilizing a height difference, or the like. Conceivable. Among these, the use of a liquid feed pump is preferable. As the devolatilizer (2), it is preferable to use a flash distillation apparatus or a film evaporator.
As the distillation column (3), a commonly used rectification column or the like is preferably used, and two or more rectification columns may be combined as necessary. Moreover, you may combine extractive distillation etc. as needed. The distillation column (3) may be one usually used for the purification of compounds, and specifically includes a plate column, a packed column, and the like.

  In the embodiment of FIG. 1, continuous volatilization means that alkylene oxide (d) is continuously added and reacted in a tubular reactor (1), and the reaction mixture (e) is fed to a feed line (6). To the devolatilizer (2) through heating and / or decompression as necessary to volatilize the by-product low boiling point compound (b) and unreacted alkylene oxide (d1), and distill through the gas phase removal line (5) It is sent to the column (3), and the alkylene oxide (d) and the by-product low boiling point compound (b) are separated in the distillation column (3). The alkylene oxide (d) is recovered through the column top line (8) (9 ) And the recovered alkylene oxide (d) may be simultaneously returned to the tubular reactor (1) through the recovered liquid feed line (10). The temperature for continuous volatilization may be a commonly performed temperature at which alkylene oxide is added. For example, it is preferably 0 to 250 ° C, more preferably 20 to 180 ° C. The degree of pressure reduction during continuous volatilization removal is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.04 MPa.

The present invention will be described based on a schematic diagram showing an example of the embodiment of the present invention shown in FIG.
In the embodiment shown in FIG. 2, by-product low boiling point during the addition polymerization of the alkylene oxide (d) to the active hydrogen-containing compound (c) in the reaction vessel (1) through the raw material supply line (4). The compound (b) and unreacted alkylene oxide (d1) are continuously or intermittently removed from the removal line (5).
First, during the reaction, part or all of the reaction mixture (e) is withdrawn continuously or intermittently from the reaction vessel (1) to the devolatilizer (2) through the feed line (6), and heated and / or if necessary. Alternatively, the pressure is reduced and the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) are volatilized continuously or intermittently and sent to the distillation column (3) through the gas phase removal line (5). The alkylene oxide (d) and the by-product low boiling point compound (b) are separated in the distillation column (3), and the alkylene oxide (d) is recovered in the recovery tank (9) through the tower top line (8). The recovered alkylene oxide (d) may be returned to the reaction vessel (1) again through the recovered liquid feeding line (10). Further, the byproduct low boiling point compound (b) is discarded through the byproduct low boiling point compound extraction line (11). After removing the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) from the reaction mixture (e), the alkylene oxide adduct is withdrawn from the recovery line (7). The alkylene oxide adduct extracted from the recovery line (7) may be subjected to addition polymerization again.

In the embodiment of FIG. 2, as a method for sending the reaction mixture (e) to the devolatilizer (2) and a method for returning the recovered alkylene oxide (d) to the reaction vessel (1) again, a liquid feed pump is used. The method of using, using a pressure difference, utilizing a height difference, etc. can be considered. Among these, the use of a liquid feed pump is preferable. As the devolatilizer (7), it is preferable to use a flash distillation apparatus, a film evaporator or the like.
As the distillation column (3), a commonly used rectification column or the like is preferably used, and two or more rectification columns may be combined as necessary. Moreover, you may combine extractive distillation etc. as needed. The distillation column (3) may be one usually used for the purification of compounds, and specifically includes a plate column, a packed column, and the like.

In the embodiment of FIG. 2, intermittent volatilization means that alkylene oxide (d) is added in 2 to 100 portions and reacted in the reaction vessel (1) and part of the reaction mixture (e). Alternatively, the entire amount is withdrawn to the devolatilizer (2) through the feed line (6) and heated and / or decompressed as necessary to volatilize the by-product low-boiling point compound (b) and unreacted alkylene oxide (d1). means. The temperature at which the volatilization is intermittently volatilized may be a usual temperature at which alkylene oxide is added. For example, it is preferably 0 to 250 ° C, more preferably 20 to 180 ° C. The degree of reduced pressure during intermittent volatilization removal is preferably 0.001 to 0.1 MPa, and more preferably 0.001 to 0.04 MPa.
Continuous volatilization removal means that alkylene oxide (d) is continuously added and reacted in the reaction vessel (1), and a part or all of the reaction mixture (e) is sent through a feed line (6) to remove the devolatilizer. Extracted into (2) and heated and / or decompressed as necessary to volatilize the by-product low-boiling point compound (b) and unreacted alkylene oxide (d1), and pass through the gas phase removal line (5) to the distillation column (3) The alkylene oxide (d) and the by-product low boiling point compound (b) are separated in the distillation column (3), and the alkylene oxide (d) is recovered in the recovery tank (9) through the tower top line (8). This means that the recovered alkylene oxide (d) may be simultaneously returned to the reaction vessel (1) through the recovered liquid feeding line (10). The temperature for continuous volatilization may be a commonly performed temperature at which alkylene oxide is added. For example, it is preferably 0 to 250 ° C, more preferably 20 to 180 ° C. The degree of pressure reduction during continuous volatilization removal is preferably 0.001 to 0.1 MPa, more preferably 0.001 to 0.04 MPa.

  When the water content of the alkylene oxide adduct is high, it 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. When it is 1000 ppm or less, the ether bond of the alkylene oxide adduct 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 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 aforementioned amino group-containing compounds 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 0.1 to 100% by weight, more preferably 1 to 20% by weight, based on the addition product. The amount of caustic alkali or amine compound used is preferably from 0.1 to 10% by weight, more preferably from 0.3 to 2% by weight, 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.)) 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, 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.

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

  In addition, the quantitative determination of the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) in the reaction mixture (e) was analyzed by headspace gas chromatography. In the measurement, the vial was kept at a temperature of 70 ° C., and the incubation time was 30 minutes.

<Example 1>
As shown in FIG. 1, a static mixer, a temperature control device, a stainless steel reaction tube as a reaction tube (1) with a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of the pipe | tube (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
The PO adduct of pentaerythritol (hydroxyl value 230) and PO are introduced into the reaction tube (1) through the raw material supply line (4) so that the respective flow ratios are 3000: 300, and the reaction temperature is 60 to 90 ° C. Controlled to keep cooling. Further, the flow rate of tris (pentafluorophenyl) borane was controlled so that the PO consumption rate at the outlet of the reaction tube (1) was 75 to 85%. Subsequently, the pentaerythritol PO adduct in the reaction tube (1) is sent to the devolatilizer (2) through the feed line (6) and reduced in pressure (0.01 MPa) by the diaphragm type vacuum pump installed in the removal line (5). After the volatile component was distilled off, the product (pentaerythritol PO adduct) devolatilized from the PPG recovery line (7) was sent to another tank, and all the reactants in the reaction tube (1) were devolatilized. The product received in a separate tank is sent to the reaction tube (1). This step is repeated until the liquid pentaerythritol PO adduct is 295 parts to 2000 parts, and then the liquid pentaerythritol PO is added. A product (A-1) was obtained.
The hydroxyl value of (A-1) was 36. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.4 to 1.0% by weight throughout the entire addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.5% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 1.5 to 3.8% by weight throughout all the steps of the addition reaction. The total time required for devolatilization was 9.6 hours. In the rectification performed during the production time, the content of alkylene oxide in the by-product low-boiling-point extraction line (11) was 3.5% by weight, and the content of alkylene oxide in the recovery tower (9) was 99.7% by weight. It was. The PO adduct of pentaerythritol used as a raw material is obtained by adding a predetermined amount of propylene oxide to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 2>
As shown in FIG. 1, a static mixer, a temperature control device, a stainless steel reaction tube as a reaction tube (1) with a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of the pipe | tube (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
The PO adduct of glycerin (hydroxyl value 280) and PO are introduced into the reaction tube (1) through the raw material supply line (4) so that the respective flow ratios are 3000: 600, and the reaction temperature is 60 to 90 ° C. Cooling control was performed to keep. Further, the flow rate of tris (pentafluorophenyl) borane was controlled so that the PO consumption rate at the outlet of the reaction tube (1) was 75 to 85%. Subsequently, the glycerin PO adduct in the reaction tube (1) is sent to the devolatilizer (2) through the feed line (6), and reduced in pressure (0.01 MPa) by the diaphragm type vacuum pump installed in the removal line (5). Volatile components were distilled off, the product (glycerin PO adduct) devolatilized from the PPG recovery line (7) was sent to another tank, and all the reactants in the reaction tube (1) were devolatilized. The product received in the tank was sent to the reaction tube (1), and this step was repeated until the liquid glycerin PO adduct amounted to 415 parts to 2000 parts, and then the liquid glycerin PO adduct (A- 2) was obtained.
The hydroxyl value of (A-2) was 61. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.5 to 1.0% by weight throughout the entire addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.7% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 2.5 to 4.2% by weight throughout all the steps of the addition reaction. The total time required for devolatilization was 7.1 hours. In the rectification conducted during the production time, the unreacted alkylene oxide content in the by-product low boiling point compound extraction line (11) was 2.2% by weight, and the alkylene oxide content in the recovery tower (9) was 99.9% by weight. Met. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of propylene oxide to glycerin using tris (pentafluorophenyl) borane as a catalyst.

<Example 3>
As in the embodiment shown in FIG. 2, a reaction vessel made of stainless steel as a reaction vessel (1) with a stirring device, a temperature control device, a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of tank (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
295 parts of PO adduct of pentaerythritol (hydroxyl value 230) is charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 1002 parts of PO are charged through the raw material supply line (4), and the reaction temperature is It added, controlling so that 60-90 degreeC might be maintained. However, the PO was added in small portions several times, 105 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (2) and installed in the removal line (5). The pressure (0.01 MPa) is reduced by a vacuum pump, the volatile component is distilled off, and the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (7) is sent to another reaction tank. After all the reaction product of (1) was devolatilized, the product received in another reaction vessel was returned to the reaction vessel (1). This process was repeated 22 times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by the devolatilizer (2) to obtain a liquid pentaerythritol PO adduct (A-3).
The hydroxyl value of (A-3) was 35. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.3 to 1.0% by weight throughout all the steps of the addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.5% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 1.2 to 2.9% by weight throughout all the steps of the addition reaction. The total time required for devolatilization was 10.1 hours. In the rectification performed during the production time, the content of unreacted alkylene oxide in the by-product low boiling point compound extraction line (11) was 3.1%, and the content of alkylene oxide in the recovery tower (9) was 99.8%. It was. The PO adduct of pentaerythritol used as a raw material is obtained by adding a predetermined amount of propylene oxide to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Comparative Example 1>
As shown in FIG. 1, a static mixer, a temperature control device, a stainless steel reaction tube as a reaction tube (1) with a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of the pipe | tube (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
The PO adduct of pentaerythritol (hydroxyl value 230) and PO are introduced into the reaction tube (1) through the raw material supply line (4) so that the respective flow ratios are 3000: 300, and the reaction temperature is 60 to 90 ° C. Controlled to keep cooling. The flow rate of tris (pentafluorophenyl) borane was controlled so that the PO consumption rate at the outlet of the reaction tube (1) was 95 to 99%. Subsequently, the pentaerythritol PO adduct in the reaction tube (1) is sent to the devolatilizer (2) through the feed line (6) and reduced in pressure (0.01 MPa) by the diaphragm type vacuum pump installed in the removal line (5). After the volatile component was distilled off, the product (pentaerythritol PO adduct) devolatilized from the PPG recovery line (7) was sent to another tank, and all the reactants in the reaction tube (1) were devolatilized. The product received in a separate tank is sent to the reaction tube (1). This step is repeated until the liquid pentaerythritol PO adduct becomes 295 parts to 2000 parts, and then the liquid pentaerythritol PO addition is performed. A product (A′-4) was obtained.
The hydroxyl value of (A′-4) was 36. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.5 to 1.5% by weight throughout the entire addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 1.1% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 0.1 wt% or more and less than 0.5 wt% throughout the entire addition reaction. The total time required for devolatilization was 19.3 hours. In the rectification performed during the production time, the alkylene oxide content in the by-product low-boiling compound extraction line (11) was 0.5% by weight, and the alkylene oxide content in the recovery tower (9) was 79.2% by weight. It was. The PO adduct of pentaerythritol used as a raw material is obtained by adding a predetermined amount of propylene oxide to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Comparative Example 2>
As shown in FIG. 1, a static mixer, a temperature control device, a stainless steel reaction tube as a reaction tube (1) with a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of the pipe | tube (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
The PO adduct of glycerin (hydroxyl value 280) and PO are introduced into the reaction tube (1) through the raw material supply line (4) so that the respective flow ratios are 3000: 600, and the reaction temperature is 60 to 90 ° C. Cooling control was performed to keep. The flow rate of tris (pentafluorophenyl) borane was controlled so that the PO consumption rate at the outlet of the reaction tube (1) was 30 to 40%. Subsequently, the glycerin PO adduct in the reaction tube (1) is sent to the devolatilizer (2) through the feed line (6), and reduced in pressure (0.01 MPa) by the diaphragm type vacuum pump installed in the removal line (5). Volatile components were distilled off, the product (glycerin PO adduct) devolatilized from the PPG recovery line (7) was sent to another tank, and all the reactants in the reaction tube (1) were devolatilized. The product received in the tank was sent to the reaction tube (1), and this step was repeated until the liquid glycerin PO adduct amounted to 415 parts to 2000 parts, and then the liquid glycerin PO adduct (A ′ -5) was obtained.
The hydroxyl value of (A′-5) was 60. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.2 to 0.8% by weight throughout the entire addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.5% by weight. The content of unreacted alkylene oxide (d1) in the reaction mixture (e) was more than 10.0% by weight and not more than 11.7% by weight throughout all the steps of the addition reaction. The total time required for devolatilization was 8.2 hours. In the rectification performed during the production time, the unreacted alkylene oxide content in the by-product low-boiling compound extraction line (11) was 42.2% by weight, and the alkylene oxide content in the recovery tower (9) was 99.9% by weight. Met. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of propylene oxide to glycerin using tris (pentafluorophenyl) borane as a catalyst.

<Comparative Example 3>
As in the embodiment shown in FIG. 2, a reaction vessel made of stainless steel as a reaction vessel (1) with a stirring device, a temperature control device, a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of tank (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
295 parts of PO adduct of pentaerythritol (hydroxyl value 230) is charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 1002 parts of PO are charged through the raw material supply line (4), and the reaction temperature is It added, controlling so that 60-90 degreeC might be maintained. However, after PO was introduced in small portions several times, 65 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (2) and installed in the removal line (5). The pressure (0.01 MPa) is reduced by a vacuum pump, the volatile component is distilled off, and the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (7) is sent to another reaction tank. After all the reaction product of (1) was devolatilized, the product received in another reaction vessel was returned to the reaction vessel (1). This process was repeated 32 times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by the devolatilizer (2) to obtain a liquid pentaerythritol PO adduct (A'-6).
The hydroxyl value of (A′-6) was 34. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.3 to 1.0% by weight throughout all the steps of the addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.5% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 0.1 wt% or more and less than 0.5 wt% throughout the entire addition reaction. The total time required for devolatilization was 18.7 hours. In the rectification performed during the production time, the content of unreacted alkylene oxide in the by-product low boiling point compound extraction line (11) was 2.1%, and the content of alkylene oxide in the recovery tower (9) was 89.6%. It was. The PO adduct of pentaerythritol used as a raw material is obtained by adding a predetermined amount of propylene oxide to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Comparative Example 4>
As in the embodiment shown in FIG. 2, a reaction vessel made of stainless steel as a reaction vessel (1) with a stirring device, a temperature control device, a raw material supply line (4), and a film evaporator as a devolatilization device (2) It connected in order of tank (1)-> feed line (6)-> devolatilizer (2). A diaphragm type vacuum pump was installed in the gas phase removal line (5) and connected in the order of the gas phase removal line (5) → distillation column (3) → column top line (8) → recovery column (9). Liquid feed pumps were installed in the raw material supply line (4) and the recovery line (7).
415 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 1870 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 60 It added, controlling so that -90 degreeC may be maintained. However, after PO was added in small portions several times, 210 parts were added, and then the PO adduct of glycerin was sent from the feed line (6) to the devolatilizer (2) and installed in the removal line (5). The pressure (0.01 MPa) was reduced by a vacuum pump, the volatile component was distilled off, and the product (PO adduct of glycerin) devolatilized from the PPG feed line (7) was sent to another reaction tank. After all the reaction product of 1) was devolatilized, the product received in another reaction vessel was returned to the reaction vessel (1). This process was repeated 9 times. PO was added until the PO adduct of liquid glycerin reached 2000 parts, and then devolatilized by the devolatilizer (2) to obtain a liquid glycerin PO adduct (A′-7).
The hydroxyl value of (A′-7) was 61. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 0.4 to 1.0% by weight throughout the entire addition reaction. Moreover, the average content of (b) throughout all the steps of the addition reaction was 0.7% by weight. The content of the unreacted alkylene oxide (d1) in the reaction mixture (e) was 0.1 wt% or more and less than 0.5 wt% throughout the entire addition reaction. The total time required for devolatilization was 15.5 hours. In the rectification conducted during the production time, the unreacted alkylene oxide content in the by-product low-boiling compound extraction line (11) was 1.9%, and the alkylene oxide content in the recovery tower (9) was 92.2%. It was. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of propylene oxide to glycerin using tris (pentafluorophenyl) borane as a catalyst.

  In Examples 1, 2, and 3 of the present invention, the quality of the resulting alkylene oxide is equivalent to that of Comparative Examples 1, 3, and 4, but the devolatilization time is less than half, Rectification of devolatilized components is completed within the production time. Moreover, compared with the comparative example 2, although the quality and devolatilization time of the alkylene oxide obtained are equivalent, the recovery rate of unreacted alkylene oxide is several times higher, and it is very excellent in terms of production efficiency.

  By the method for producing an alkylene oxide adduct of the present invention, low boiling point volatile components can be easily devolatilized, and unreacted alkylene oxide can be easily separated and recovered and reused, thereby improving production efficiency. .

1 reaction tube (tank)
2 Devolatilizer 3 Distillation tower 4 Raw material supply line 5 Removal line 6 Feed line 7 Recovery line 8 Tower top line 9 Recovery tank 10 Recovery liquid feed line 11 By-product low boiling point compound extraction line

Claims (4)

  A process for producing an alkylene oxide adduct, wherein a reaction mixture (e) obtained by adding an alkylene oxide (d) to an active hydrogen-containing compound (c) in the presence of a Lewis acid catalyst (a) is removed from a reactor. The step of separating the unreacted alkylene oxide (d1) and the by-product low boiling point compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa from the reaction mixture (e), The manufacturing method of the alkylene oxide adduct whose content of the unreacted alkylene oxide (d1) in it is 0.5 to 10 weight% on the basis of the weight of (e).   The weight ratio [(b) / (d1)] of the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1) in the reaction mixture (e) is 1/1 to 1/10. The manufacturing method as described.   The production method according to claim 1 or 2, wherein the reactor is a tubular reactor.   The alkylene oxide (d) in the process contains the regenerated alkylene oxide (d2) obtained by rectifying the mixture of the separated by-product low boiling point compound (b) and the unreacted alkylene oxide (d1). Item 4. The production method according to any one of Items 1 to 3.

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