JP5291737B2 - Method for producing alkylene oxide adduct - Google Patents

Description

  The present invention relates to a method for producing an alkylene oxide adduct and a method for producing a polyurethane resin using an alkylene oxide adduct obtained by the production method.

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

  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. In addition, polyurethane resins and polyurethane foams produced using alkylene oxide adducts containing by-product low-boiling volatile components generate unpleasant odors, and a post-treatment step is required to remove the odors. There is a problem. Although it is known that odor can be reduced by using a specific Lewis acid catalyst (see Patent Document 1), the number average functional group number is lowered, and the effect of odor reduction is insufficient. Further, odor can be reduced by addition polymerization of an active hydrogen-containing compound with an alkylene oxide while continuously or intermittently removing the by-product low-boiling compound (b) in the presence of a Lewis acid catalyst. Although known to be present (see Patent Document 2), the number-average functional group number decreases.

JP 2003-183383 A JP 2009-227978 A

  An object of this invention is to provide the manufacturing method of the alkylene oxide adduct which does not require the post-processing process which removes a low boiling-point volatile component, and improved the fall of the number average functional group number.

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 presence of a Lewis acid catalyst (a), Oite the reaction of adding an alkylene oxide (d) the active hydrogen-containing compound (c), are reacted with added dividedly 2 to 100 times (d) is it and made from the liquid phase, or liquid phase and the reaction mixture consisting of the gas phase from (e), another device has a boiling point 0.99 ° C. or less of the byproduct low-boiling compounds and (b) a reactor at a pressure 0.1MPa And a method for producing an alkylene oxide adduct comprising a step of repeating the step of intermittent removal .
(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. The gist is to use the alkylene oxide adduct obtained by the production method of (I) above.

  According to the method for producing an alkylene oxide adduct of the present invention, a post-treatment step for removing low boiling point volatile components is not required, and a decrease in the number average functional group number can be suppressed.

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 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: 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 Japanese Patent Publication 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 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 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), 1,3-propylene oxide, 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 and block addition in the case of using two or more types of (d).

  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 comprises the following step (1).
Step (1): a reaction mixture (e) in a reaction of adding an alkylene oxide (d) to an active hydrogen-containing compound (c) in the presence of a Lewis acid catalyst (a), consisting of a liquid phase, or a liquid phase And a by-product low-boiling compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa from the reaction mixture (e) comprising the gas phase.

  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 carrying out the step of removing (b) 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 a part of the reaction mixture (e) is a gas phase. When the step of removing (b) is carried out at a temperature and a pressure, the reaction mixture (e) is a mixture composed of a liquid phase and a gas phase.

  Step (1) may be performed simultaneously with the step of adding alkylene oxide (d) to active hydrogen compound (c), that is, while adding (d), or may be performed as a separate step.

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 and a method for separating (b) by adsorbing the adsorbent (f). These may be performed in combination.
From the viewpoint of facilitating separation by distillation, the by-product low-boiling compound (b) is brought into contact with the solid catalyst (g), and the by-product low-boiling compound (b) is reacted to have a higher boiling point (h) And then may be separated.

  The reaction vessel used for 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 it can withstand a pressure of 1 MPa and is heated. It is also desirable to be able to cool and be equipped with a stirring device. Examples of the material for the reaction tank include glass, iron, stainless steel, aluminum, various alloys, and carbon. Stainless steel having corrosion resistance is preferable.

  When (b) is separated by an apparatus different from the reaction tank, the temperature of the reaction tank when the reaction mixture (e) is sent to another apparatus may be a temperature at which the alkylene oxide (d) is subjected to addition polymerization. 250 degreeC is preferable, More preferably, it is 20-180 degreeC.

  When (b) is separated in an apparatus separate from the reaction tank, the pressure in the reaction tank when the reaction mixture (e) is sent to another apparatus is such that the alkylene oxide (d) is added, the reactivity of the addition polymerization, and From the viewpoint of easy removal of the gas phase, it is preferably 1 MPa or less, more preferably 0.0001 to 0.1 MPa, and further preferably 0.001 to 0.08 MPa for more aggressive gas phase removal. It is.

  In the present invention, when the by-product low-boiling-point compound (b) is adsorbed and separated by the adsorbent (f), the adsorption tower used at that time can be filled with the adsorbent and adsorbed when vented to the adsorption tower. The container is not particularly limited as long as the agent does not diffuse out of the container, but is preferably provided with a temperature adjusting means (heating and cooling) and / or a pressure adjusting means (pressurizing and depressurizing), and the material is corrosion resistant. Stainless steel with properties is desirable.

  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 manufacturing method of this invention, two or more processes (1) may be included, and it is preferable to include 2-15 processes (1) from a viewpoint of improvement of the fall of a number average functional group number.

In the production method of the present invention, the content of the by-product low-boiling compound (b) in the reaction mixture (e) is ( Based on the weight of e), it is preferably 10% by weight or less, more preferably 8% by weight or less, and still more preferably 6% by weight or less.
In addition, content of (b) can be measured with normal measuring methods, such as a gas chromatography.

In the production method of the present invention, from the viewpoint of reducing the number average functional group number of alkylene oxide and the content of unsaturated groups by-produced, the average content of the by-product low-boiling compound (b) in the reaction mixture (e) is: Based on the weight of (e), it is preferably 5% by weight or less, more preferably 2% by weight or less, and still more preferably 1% by weight or less.
In the above and below, the average content of the by-product low-boiling compound (b) is the average content over the reaction 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, 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 continuously or intermittently sent from the reaction vessel (1) to the devolatilizer (7) 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 unreacted alkylene oxide (d1) are volatilized continuously or intermittently and removed from the reaction system through the removal line (5). After removing the by-product low boiling point compound (b) and the unreacted alkylene oxide (d1), the alkylene oxide adduct is withdrawn from the recovery line (8). The alkylene oxide adduct extracted from the recovery line (8) may be subjected to addition polymerization again.

  In the embodiment of FIG. 1, as a method of sending the reaction mixture (e) to the devolatilizer (7), a method of using a liquid feed pump, 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.

In the embodiment of FIG. 1, 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 sent to the devolatilizer (7) 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), What is necessary is just to repeat removing out of a reaction system through a phase removal line (5). 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 the alkylene oxide (d) is reacted in the reaction vessel (1), and a part or all of the reaction mixture (e) is extracted to the devolatilizer (7) through the feed line (6). If necessary, heating and / or decompressing is performed to volatilize the by-product low-boiling compound (b) and unreacted alkylene oxide (d1), and simultaneously remove them from the reaction system through the gas phase removal line (5). Means that. 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 reduced pressure during intermittent volatilization removal is preferably 0.001 to 0.1 MPa, and 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) through the feed line (6) to the devolatilizer (7), 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 (10) through the column top line (9). The recovered alkylene oxide (d) may be returned again to the reaction vessel (1) through the recovered liquid feeding line (11). Further, the byproduct low boiling point compound (b) is discarded through the byproduct low boiling point compound extraction line (12). 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 (8). The alkylene oxide adduct extracted from the recovery line (8) 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 (7) 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 (7) 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 (7), heated and / or decompressed as necessary to volatilize the by-product low-boiling point compound (b) and unreacted alkylene oxide (d1), and distilled through the vapor phase removal line (5) (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 (10) through the column top line (9). . It means that the recovered alkylene oxide (d) may be simultaneously returned to the reaction vessel (1) through the recovered liquid feeding line (11). 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.
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 Oxide (d1) is removed continuously or intermittently from 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) through the feed line (6) to the devolatilizer (7), 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 adsorption tower (2) through the removal line (5). In the adsorption tower (2), the alkylene oxide (d) and the by-product low boiling point compound (b) are adsorbed on the adsorbent (e) packed in the adsorption tower (2), and the alkylene oxide ( d2) is returned to the reaction tank (1) again continuously or intermittently through the circulation line (13). During the reaction and / or after completion of the reaction, the adsorption tower (2) and the devolatilizer (7) are shut off by valves provided in the gas phase removal line (5) and the circulation line (13), and the adsorption tower (2) is heated. And / or by depressurizing, the alkylene oxide (d3) adsorbed on (b) and the adsorbent (e) is desorbed from the adsorbent (e). (B) and (d3) desorbed from the adsorbent (e) are sent to the distillation column (3) through the recovery line 2 (82), and after separating the compound having a higher boiling point from the alkylene oxide (d), It collects in a recovery tank (10) through a line (9). The recovered alkylene oxide (d) may be returned again to the reaction vessel (1) through the recovered liquid feeding line (11). Further, the byproduct low boiling point compound (b) is discarded through the byproduct low boiling point compound extraction line (12). 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 (8). The alkylene oxide adduct extracted from the recovery line (8) may be subjected to addition polymerization again.

In the embodiment of FIG. 3, as a method for sending the reaction mixture (e) to the devolatilizer (7) 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.

  Method of sending gas phase (i) containing by-product low boiling point compound (b) and unreacted alkylene oxide (d1) to adsorption tower (2), adsorbed alkylene oxide (d2) to adsorption tower (2) The method of returning from the reactor to the reaction vessel (1) and the method of sending the adsorbed alkylene oxide (d3) to the distillation column (3) include a method utilizing a pressure difference, and a vacuum pump or blower can be used. Other methods may be used.

  A method of charging the alkylene oxide (d) into the reaction vessel (1), a method of sending the recovered alkylene oxide (d4) to the recovery vessel (10), and a method of sending the recovered alkylene oxide (d4) to the reaction vessel (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.

  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 adsorbing tower (2) is not particularly limited as long as it can be filled with an adsorbent therein and the adsorbent does not diffuse outside the container when vented to the adsorbing tower. Cooling) and / or a material provided with pressure adjusting means (pressurization and decompression) is desirable, and the material is preferably stainless steel having corrosion resistance.

  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 (f) packed 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 (f) is preferably 1 to 3000 times, particularly preferably 10 to 2000 times the generated weight of the by-product low-boiling compound (b).

In the embodiment of the present invention shown in FIG. 3, intermittent volatilization removal means that alkylene oxide (d) is added in 2 to 100 times and reacted in a reaction vessel (1), and a reaction mixture ( A part or all of e) is withdrawn to the devolatilizer (7) through the feed line (6), and heated and / or decompressed as necessary to produce a by-product low-boiling compound (b) and unreacted alkylene oxide (d1) Is volatilized. 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 (7), heated and / or decompressed as necessary to volatilize the by-product low-boiling point compound (b) and unreacted alkylene oxide (d1), and sent to the adsorption tower (2) through the removal line (5). The alkylene oxide (d) and the by-product low boiling point compound (b) are adsorbed on the adsorbent (e) packed in the adsorption tower (2), and the alkylene oxide (d2) not adsorbed on the adsorbent is circulated in the circulation line. Return to the tank (1) again continuously or intermittently through (13). During the reaction and / or after completion of the reaction, the adsorption tower (2) and the devolatilizer (7) are shut off with valves provided in the removal line (5) and the circulation line (13), and the adsorption tower (2) is heated and By depressurizing, the alkylene oxide (d3) adsorbed on (b) and the adsorbent (e) is desorbed from the adsorbent (e). (B) and (d3) desorbed from the adsorbent (e) are sent to the distillation column (3) through the recovery line 2 (82), and after separating the compound having a higher boiling point from the alkylene oxide (d), It collects in a recovery tank (10) through a line (9). It means that the recovered alkylene oxide (d) may be simultaneously returned to the reaction vessel (1) through the recovered liquid feeding line (11). 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.
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 Oxide (d1) is removed continuously or intermittently from 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) through the feed line (6) to the devolatilizer (7), 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 reaction tower (14) through the removal line (5). The solid catalyst (g) packed in the reaction tower (14) and the by-product low boiling point compound (b) are brought into contact with each other to change to a compound (h) having a higher boiling point. After the gas phase containing (h) and the unreacted alkylene oxide (d1) is sent to the distillation column (3) through the recovery line 2 (82), a compound having a higher boiling point than the alkylene oxide (d) is separated, It collects in a recovery tank (10) through a tower top line (9). The recovered alkylene oxide (d) may be returned again to the reaction vessel (1) through the recovered liquid feeding 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 (8). The alkylene oxide adduct extracted from the recovery line (8) may be subjected to addition polymerization again.

In the embodiment of FIG. 4, as a method of sending the reaction mixture (e) to the devolatilizer (7), a method of using a liquid feed pump, utilizing 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. 4, the reaction tower (14) used when the by-product low-boiling compound (b) is brought into contact with the solid catalyst (g) can be filled with the solid catalyst (g), and the reaction tower (14 Is not particularly limited as long as the solid catalyst (g) does not diffuse out of the container when it is ventilated), but it is desirable that it can be heated and cooled and / or pressurized or depressurized. Is preferably stainless steel with corrosion resistance.

  The compound (h) having a higher boiling point obtained by reacting the by-product low boiling point compound (b) includes 2-methyl-2-pentenal (boiling point 137 ° C.), water (boiling point 100 ° C.), propylene alcohol, allyl. Alcohols, allyl aldehydes, acrylic acid, acrylic esters and the like are included.

  The solid catalyst (g) used when the gas phase containing the by-product low-boiling compound (b) and the unreacted alkylene oxide (d1) is brought into contact with the solid catalyst (g) includes alkalis such as sodium, potassium and lithium. Examples thereof include metals, alkaline earth metals such as calcium and magnesium, and oxides, carbonates, sulfides and other metal salts of these metals. Other examples include complex oxides, alloys, and heteropolyacids. Metal oxides and metal carbonates are preferably used as the solid catalyst (g), and magnesium oxide is particularly preferable, but is not limited thereto. It is not something.

In the embodiment of the present invention shown in FIG. 4, intermittent volatilization removal means that alkylene oxide (d) is added in 2 to 100 times and reacted in a reaction vessel (1), and a reaction mixture ( A part or all of e) is withdrawn to the devolatilizer (7) through the feed line (6), and heated and / or decompressed as necessary to produce a by-product low-boiling compound (b) and unreacted alkylene oxide (d1) Is volatilized. 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 (7), heated and / or decompressed as necessary to volatilize the by-product low boiling point compound (b) and unreacted alkylene oxide (d1), and sent to the reaction tower (14) through the removal line (5). The solid catalyst (g) charged with the alkylene oxide (d) and the by-product low-boiling compound (b) in the reaction tower (14) and the by-product low-boiling compound (b) are brought into contact with each other to have a higher boiling point. Change to compound (h). The gas phase (i) containing (h) and unreacted alkylene oxide (d1) is sent to the distillation column (3) through the recovery line 2 (82) to separate compounds having a higher boiling point than the alkylene oxide (d). Then, it is recovered in the recovery tank (10) through the tower top line (9). It means that the recovered alkylene oxide (d) may be simultaneously returned to the reaction vessel (1) through the recovered liquid feeding line (11).
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.

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, a moisture adsorption tower (15) is provided between the recovered liquid feeding line (11) and the reaction vessel (1). ).

  The adsorbent filled in the moisture adsorption tower (15) may be the same as the adsorbent (f) used in the adsorption tower. Specifically, it 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 (f) is preferably 1 to 3000 times, particularly preferably 10 to 2000 times the generated weight of the by-product low-boiling compound (b).

  Two or more moisture adsorption towers (15) may be used as needed, and each may be operated simultaneously or alternately. The moisture adsorption tower (15) is not particularly limited as long as it can be filled with an adsorbent, and the adsorbent does not diffuse out of the container when vented to the adsorption tower. And cooling) and / or pressure adjusting means (pressurization and decompression) are desirable, and the material is preferably stainless steel having corrosion resistance.

  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.

  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. 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 alkylene oxide adduct (A) (particularly a divalent to octavalent or higher alkylene oxide adduct) obtained by the production method of the present invention can be used for various applications, but produces a foamed or non-foamed polyurethane resin. It is used suitably for doing.
That is, when the foam component or the non-foamed polyurethane resin is produced by reacting the polyol component and the organic polyisocyanate (C) in the presence of an additive as necessary, the production method of the present invention is used as at least a part of the polyol component. The obtained alkylene oxide adduct (A) can be used. The use of the alkylene oxide adduct obtained by the production method of the present invention includes the use of the polymer alcohol (B) obtained by polymerizing the vinyl monomer (m) in the alkylene oxide adduct. It is.

  The polymer alcohol (B) can be produced by polymerizing a vinyl monomer in a usual manner in the alkylene oxide adduct (A). 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, 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.

<Example 1>
As in the embodiment shown in FIG. 1, a stainless steel reaction vessel 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 (7) are reacted. It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
295 parts of a pentaerythritol PO adduct (hydroxyl value 230) was charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 2160 parts of PO were charged through the raw material supply line (4), and the reaction temperature was It added, controlling so that 75-90 degreeC might be maintained. However, after PO was introduced in small portions several times, 720 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The pressure was reduced (0.01 MPa) with a mold vacuum pump, the volatile component was distilled off, and the process was sent from the PPG feed line (8) to the reaction vessel. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by the devolatilizer (7) to obtain a liquid pentaerythritol PO adduct (A-1). The hydroxyl value was 38, the number average functional group number was 3.0, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 10% by weight or less and may be 10.0% by weight throughout all the steps of the addition reaction. Further, the average content throughout all the steps of the addition reaction was 4.5% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 2>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
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 75-90 degreeC might be maintained. However, after pouring PO into several portions in small portions, 190 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The pressure was reduced (0.01 MPa) with a mold vacuum pump, the volatile component was distilled off, and the process was sent from the PPG feed line (8) to the reaction vessel, and this process was repeated 10 times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by a devolatilizer (7) to obtain a liquid pentaerythritol PO adduct (A-2). The hydroxyl value was 36, the number average functional group number was 3.4, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 2.0% by weight or less and may be 2.0% by weight throughout the addition reaction. Moreover, the average content throughout all the steps of the addition reaction was 1.5% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 3>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
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 75-90 degreeC might be maintained. However, after pouring PO into several portions in small portions, 190 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). Reduced pressure (0.01 MPa) with a mold vacuum pump, volatile components were distilled off, and the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (8) 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 10 times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by a devolatilizer (7) to obtain a liquid pentaerythritol PO adduct (A-3). The hydroxyl value was 36, the number average functional group number was 3.4, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 2.0% by weight or less and may be 2.0% by weight throughout the addition reaction. Further, the average content throughout all the steps of the addition reaction was 1.0% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 4>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
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 75-90 degreeC might be maintained. However, the PO was introduced in several small portions, 65 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing the pressure (0.01 MPa) with a mold vacuum pump, distilling off the volatile components, and sending the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (8) to another reaction vessel, After all the reactants in the reaction vessel (1) were 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 (7) to obtain a liquid pentaerythritol PO adduct (A-4). The hydroxyl value was 34, the number average functional group number was 3.7, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 1.0% by weight or less and may be 1.0% by weight throughout all the steps of the addition reaction. Further, the average content throughout all the steps of the addition reaction was 0.5% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 5>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
295 parts of a pentaerythritol PO adduct (hydroxyl value 230) was charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 2160 parts of PO were charged through the raw material supply line (4), and the reaction temperature was It added, controlling so that 75-90 degreeC might be maintained. However, after PO was introduced in small portions several times, 720 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing the pressure (0.01 MPa) with a mold vacuum pump, distilling off the volatile components, and sending the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (8) to another reaction vessel, After all the reactants in the reaction vessel (1) were devolatilized, the product received in another reaction vessel was returned to the reaction vessel (1). This process was repeated three times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by a devolatilizer (7) to obtain a liquid pentaerythritol PO adduct (A-5). The hydroxyl value was 38, the number average functional group number was 3.0, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 10% by weight or less and may be 10.0% by weight throughout all the steps of the addition reaction. Further, the average content throughout all the steps of the addition reaction was 4.5% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 6>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
415 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction tank (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 75. It added, controlling so that -90 degreeC may be maintained. However, PO was added in small portions several times, and 210 parts were added, and then the PO adduct of glycerin was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing pressure (0.01 MPa) with a vacuum pump, distilling off volatile components, and sending the product (PO adduct of glycerin) devolatilized from the PPG feed line (8) to another reaction vessel, reaction After all the reaction products in the tank (1) were devolatilized, the product received in another reaction tank was returned to the reaction tank (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 (7) to obtain a liquid glycerin PO adduct (A-6). The hydroxyl value was 61, the number average functional group number was 2.8, and the content of unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 1.0% by weight or less and may be 1.0% by weight throughout all the steps of the addition reaction. Moreover, the average content throughout all the steps of the addition reaction was 0.7% by weight. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of PO to glycerin using tris (pentafluorophenyl) borane as a catalyst.

<Example 7>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
410 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction tank (1), 0.09 part of tris (pentafluorophenyl) borane and 1900 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 75. It added, controlling so that -90 degreeC may be maintained. However, the PO was added in small portions several times, and 635 parts were added, and then the glycerin PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing pressure (0.01 MPa) with a vacuum pump, distilling off volatile components, and sending the product (PO adduct of glycerin) devolatilized from the PPG feed line (8) to another reaction vessel, reaction After all the reaction products in the tank (1) were devolatilized, the product received in another reaction tank was returned to the reaction tank (1). This process was repeated three times. PO was added until the PO adduct of liquid glycerin reached 2000 parts, and then devolatilized by the devolatilizer (7) to obtain a liquid glycerin PO adduct (A-7). The hydroxyl value was 63, the number average functional group number was 2.7, and the content of unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 3.0% by weight or less and may be 3.0% by weight throughout the addition reaction. Moreover, the average content through all the steps of addition reaction was 2.0 weight%. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of PO to glycerin using tris (pentafluorophenyl) borane as a catalyst.

<Example 8>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
Charge 500 parts of a PO adduct of pentaerythritol (hydroxyl value 230) to the reaction vessel (1), add 0.09 part of tris (pentafluorophenyl) borane and 1770 parts of PO through the raw material supply line (4), and the reaction temperature is It added, controlling so that 75-90 degreeC might be maintained. However, after PO was added in small portions several times, 220 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing the pressure (0.01 MPa) with a mold vacuum pump, distilling off the volatile components, and sending the product (PO adduct of pentaerythritol) devolatilized from the PPG feed line (8) to another reaction vessel, After all the reactants in the reaction vessel (1) were devolatilized, the product received in another reaction vessel was returned to the reaction vessel (1). This process was repeated 8 times. PO was added until the liquid pentaerythritol PO adduct reached 2000 parts, and then devolatilized by a devolatilizer (7) to obtain a liquid pentaerythritol PO adduct (A-8). The hydroxyl value was 56, the number average functional group number was 3.7, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 1.5% by weight or less and sometimes 1.5% by weight throughout the entire addition reaction. Further, the average content throughout all the steps of the addition reaction was 1.0% by weight. The PO product of pentaerythritol used as a raw material is a product obtained by adding a predetermined amount of PO to pentaerythritol using tris (pentafluorophenyl) borane as a catalyst.

<Example 9>
As in the embodiment shown in FIG. 1, 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 devolatilizer (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
240 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction tank (1), 0.09 part of tris (pentafluorophenyl) borane and 2150 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 75. It added, controlling so that -90 degreeC may be maintained. However, the PO was charged in small portions several times and 135 parts were added, and then the pentaerythritol PO adduct was sent from the feed line (6) to the devolatilizer (7) and installed in the removal line (5). The process of reducing pressure (0.01 MPa) with a vacuum pump, distilling off volatile components, and sending the product (PO adduct of glycerin) devolatilized from the PPG feed line (8) to another reaction vessel, reaction After all the reaction products in the tank (1) were devolatilized, the product received in another reaction tank was returned to the reaction tank (1). This process was repeated 16 times. PO was added until the liquid glycerin PO adduct reached 2000 parts, and then devolatilized by the devolatilizer (7) to obtain a liquid glycerin PO adduct (A-9). The hydroxyl value was 39, the number average functional group number was 2.7, and the content of unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 1.5% by weight or less and sometimes 1.5% by weight throughout the entire addition reaction. Further, the average content throughout all the steps of the addition reaction was 1.0% by weight. The PO adduct of glycerin used as a raw material is obtained by adding a predetermined amount of PO to glycerin using tris (pentafluorophenyl) borane as a catalyst.

<Comparative Example 1>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
1830 parts of PO adduct of pentaerythritol (hydroxyl value 35.6) is charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 200 parts of PO are added through the raw material supply line (4), and the reaction is performed. While controlling so that the temperature was maintained at 75 to 90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid pentaerythritol PO adduct (N-1). The hydroxyl value was 38, the number average functional group number was 2.8, and the content of unsaturated group-containing material was 2.9% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 2.0% by weight or less and sometimes 2.0% by weight in the addition reaction step. Moreover, the average content throughout all the steps of the addition reaction was 1.5% by weight. The PO adduct of pentaerythritol used as a raw material was synthesized by a known method, that is, after adding a predetermined amount of PO to pentaerythritol using potassium hydroxide as a catalyst, water and synthetic silicic acid were used for catalyst removal. Salt (Kyowa Chemical Co., Ltd. Kyoward 600) was added, heat-treated, filtered, and dehydrated under reduced pressure.

<Comparative example 2>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
1660 parts of glycerin PO adduct (hydroxyl value 66) was charged into the reaction tank (1), 0.09 part of tris (pentafluorophenyl) borane and 415 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 75. While controlling so as to maintain ˜90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid glycerin PO adduct (N-2). The hydroxyl value was 61, the number average functional group number was 2.5, and the content of unsaturated group-containing material was 2.4% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 2.0% by weight and sometimes 2.0% by weight in the addition reaction step. Moreover, the average content throughout all the steps of the addition reaction was 1.5% by weight. The glycerin PO adduct used as a raw material was synthesized by a known method, that is, after adding a predetermined amount of PO to glycerin using potassium hydroxide as a catalyst, water and synthetic silicate ( Kyowa Chemical Co., Ltd. Kyoword 600) is added, heat-treated, filtered, and dehydrated under reduced pressure.

<Comparative Example 3>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
290 parts of PO adduct of pentaerythritol (hydroxyl value 230) is charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 2340 parts of PO are charged through the raw material supply line (4), and the reaction temperature is While controlling to maintain 75 to 90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid pentaerythritol PO adduct (N-3). The hydroxyl value was 41, the number average functional group number was 2.7, and the content of unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 15.5% by weight or less in the addition reaction step, sometimes 15.5% by weight. Moreover, the average content throughout all the steps of the addition reaction was 10.5% by weight.

<Comparative example 4>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
415 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction tank (1), 0.09 part of tris (pentafluorophenyl) borane and 1970 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 75. While controlling so as to maintain ˜90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid glycerin PO adduct (N-4). The hydroxyl value was 67, the number average functional group number was 2.5, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) was 8.0% by weight or less and sometimes 8.0% by weight in the addition reaction step. In addition, the average content throughout all the steps of the addition reaction was 5.5% by weight.

<Comparative Example 5>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
520 parts of a pentaerythritol PO adduct (hydroxyl value 230) was charged into the reaction vessel (1), 0.09 part of tris (pentafluorophenyl) borane and 1830 parts of PO were charged through the raw material supply line (4), and the reaction temperature was While controlling to maintain 75 to 90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid pentaerythritol PO adduct (N-5). The hydroxyl value was 58, the number average functional group number was 3.2, and the content of unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 7.5% by weight or less in the addition reaction step, and may be 7.5% by weight. In addition, the average content throughout all the steps of the addition reaction was 5.5% by weight.

<Comparative Example 6>
As in the embodiment shown in FIG. 1, 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 (7) It connected in order of the tank (1)-> feed line (6)-> devolatilizer (7). A diaphragm type vacuum pump was installed in the removal line (5). A liquid feed pump was installed in the feed line (6) and the recovery line (8).
250 parts of glycerin PO adduct (hydroxyl value 280) was charged into the reaction tank (1), 0.09 part of tris (pentafluorophenyl) borane and 2360 parts of PO were charged through the raw material supply line (4), and the reaction temperature was 75. While controlling so as to maintain ˜90 ° C., PO was added until the amount of liquid in the reaction vessel reached 2000 parts. The reaction mixture was devolatilized with a devolatilizer to obtain a liquid glycerin PO adduct (N-6). The hydroxyl value was 55, the number average functional group number was 2.3, and the content of the unsaturated group-containing material was 0.0% by weight. The content of the by-product low-boiling compound (b) in the reaction mixture (e) is 15.0% by weight or less in the addition reaction step, and may be 15.0% by weight. Moreover, the average content throughout all the steps of the addition reaction was 10.5% by weight.

Examples 1 to 5 of the present invention have the same hydroxyl value as Comparative Examples 1 and 3, but have a high number average functional group number. Production efficiency is equivalent. In particular, Example 4 is extremely excellent in terms of the number average functional group number.
Examples 6 and 7 have the same hydroxyl value as Comparative Examples 2 and 4, but the number average functional group number is high and excellent. Production efficiency is equivalent. In particular, Example 6 is extremely excellent in terms of the number average functional group number.
In Example 8 of the present invention, the hydroxyl value is equivalent to that of Comparative Example 5, but the number average functional group number is high and excellent. Production efficiency is equivalent.
Example 9 of the present invention is superior to Comparative Example 6 in that the hydroxyl value is equivalent, but the number-average functional group number is high. Production efficiency is equivalent.
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 can be seen that the examples of the present invention have a higher number average functional group number than the comparative examples, and at least one of the production efficiencies is equal to or higher than that of the comparative example.

  In accordance with the foaming formulation shown in Table 1, the polyurethane mold foam was foamed by the following foaming method example, and after standing for a day and night, various properties of the polyurethane mold foam were measured. The measured values of physical properties are also shown in Table 1. The core density is a density measured by cutting out from the center of the foam into a size of 100 mm × 100 mm × 50 mm.

<Foaming method>
An alkylene oxide adduct (A), a foaming agent (D), a urethanization catalyst catalyst (E), a foam stabilizer (F), and other auxiliary components as necessary are mixed and stirred in predetermined amounts to obtain a polyol premix. Subsequently, this polyol premix and organic polyisocyanate (C) are rapidly mixed using a polyurethane foaming machine or a stirrer. The obtained mixed solution is poured into a mold (for example, 15 to 70 ° C.) and demolded after a predetermined time to obtain a flexible polyurethane mold foam.

The raw materials of the polyurethane mold foam in the examples and comparative examples are as follows.
1. Alkylene oxide adduct (A)
1. alkylene oxide adducts prepared in Examples 3, 4, 5 and Comparative Examples 1, 3. Active hydrogen compounds other than alkylene oxide adduct (A) (c)
(1) Active hydrogen compound (c-1): PO · EO block adduct of glycerin. Hydroxyl value = 28.0, EO unit content = 16.0%, primary hydroxylation rate = 82%
(2) Active hydrogen compound (c-2): a polymer polyol obtained by copolymerizing styrene and acrylonitrile (mass ratio: 30/70) in an active hydrogen compound. (Polymer content 30.0%, hydroxyl value = 22.0 Volume average particle diameter of polymer fine particles = 0.4 μm)
The volume average particle diameter was measured by the following method. 30 ml of methanol was put into a 50 ml glass beaker, 2 mg of polymer polyol was added, and the mixture was stirred and mixed with a magnetic stirrer at 400 rpm × 3 minutes using a stirrer piece having a major axis of 2 cm and a minor axis of 0.5 cm. After mixing, the mixture was put into a measurement cell within 5 minutes, and the volume average particle diameter was measured on a volume basis using a laser diffraction / scattering particle size distribution analyzer [model number: LA-750, manufactured by Horiba, Ltd.].
(3) Active hydrogen compound (c-3): PO · EO random adduct of glycerin. Hydroxyl value = 24.0, EO unit content = 72.0%, primary hydroxylation rate = 30%
(4) Active hydrogen compound (c-4): glycerin. Hydroxyl value = 1830
(5) Active hydrogen compound (c-5): triethanolamine. Hydroxyl value = 1130
3. Urethane catalyst (E)
(1) Urethane catalyst E-1: “DABCO-33LV” (33% by weight dipropylene glycol solution of triethylenediamine) manufactured by Air Products Japan Co., Ltd.
(2) Urethane catalyst E-2: "TOYOCAT ET" manufactured by Tosoh Corporation {70% by weight dipropylene glycol solution of bis (dimethylaminoethyl) ether}
4). Foam stabilizer (F)
(1) Foam stabilizer F-1: “SZ-1346” manufactured by Toray Dow Corning Co., Ltd.
5. Foaming agent (D)
(1) Foaming agent (D): water Organic polyisocyanate component (B)
(1) Organic polyisocyanate B-1: “Cosmonate TM-20” manufactured by Mitsui Chemicals, Inc. (TDI-80 (2,4- and 2,6-TDI, ratio of 2,4-isomer is 80% by weight) ) / Crude MDI (average functional group number: 2.9) = 80/20 (weight ratio) (NCO%: 44.6%))

The measurement and evaluation methods in the examples are as follows.
<Physical property test>
<1>: Total density (kg / m ³ )
<2>: Core density (kg / m ³ )
<3>: Foam hardness (kgf / 314 cm ² )
<4>: Rebound resilience (%)
<5>: Growth rate (%)
<6>: Compression residual strain rate (%)
<1> to <6> conformed to JIS K 6400 (2004 edition).
<7>: Wet heat compression residual strain ratio (%)
In the test <7>, the temperature was 50 ° C. and the humidity was 95%.
<8>: Cure property Immediately after foam removal, the end is pinched with a finger for 10 seconds,
Things without finger marks left
Fingerprint remains ： ×
As evaluated.

  From the above results, the foams of Examples 10 to 12 obtained by the production method of the present invention had the same or better foam hardness, rebound resilience at lower core density than the foams of Comparative Examples 7 and 8. A compression residual strain rate and a wet heat compression residual strain rate can be obtained.

  According to the foaming formulation shown in Table 2, polyurethane slab foam was foamed under the following foaming conditions, and after standing for one day and night, various properties of the polyurethane slab foam were measured. The measured values of physical properties are also shown in Table 2.

<Foaming conditions>
BOX SIZE: 30cm x 30cm x 30cm Empty box Material: Wood Mixing method: Hand mixing

The raw materials of the polyurethane mold foam in the examples and comparative examples are as follows.
1. Alkylene oxide adduct (A)
1. Alkylene oxide adducts produced in Examples 6 and 7 and Comparative Examples 2 and 4. Urethane catalyst (E)
(1) Urethane catalyst E-2: “TOYOCAT ET” manufactured by Tosoh Corporation {70% by weight dipropylene glycol solution of bis (dimethylaminoethyl) ether}
(2) Urethane catalyst E-3: “Neostan U-28” (Stanus octoate) manufactured by Nitto Kasei Co., Ltd.
3. Foam stabilizer (F)
(1) Foam stabilizer F-2: “L-540” manufactured by Toray Dow Corning Co., Ltd.
4). Foaming agent (D)
(1) Foaming agent (D): water Organic polyisocyanate component (B)
(1) Organic polyisocyanate B-2: “Coronate T-80” manufactured by Nippon Polyurethane Industry Co., Ltd. (TDI-80 (2,4- and 2,6-TDI, 2,4-body)

The measurement and evaluation methods in the examples are as follows.
<Physical property test>
<1>: Core density (kg / m ³ )
<2>: Foam hardness (kgf / 314 cm ² )
<3>: Rebound resilience (%)
<4>: Growth rate (%)
<5>: Compression residual strain rate (%)
<1> to <5> are based on JIS K 6400 (2004 edition).
<6>: Wet heat compression residual strain ratio (%)
In the test <6>, the temperature was 50 ° C. and the humidity was 95%.
<7>: Breathability (cc / cm / sec)
<7> conforms to JIS L1004

  From the results shown in Table 2, the foams of Examples 13 and 14 obtained by the production method of the present invention are equivalent to or higher than the foams of Comparative Examples 9 and 10 in foam hardness, impact resilience, elongation, and compression residual strain. Ratio, wet heat compression residual strain ratio.

<Example 15>
Addition of 3,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) 103g, alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500ml stirrer and temperature controller 410 g of product (A-3), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Example 16>
Addition of 3,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) 103g, alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500ml stirrer and temperature controller 410 g of product (A-4), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Example 17>
Addition of 160 g of 4,4′-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500 ml stirring device and a temperature control device 410 g of product (A-7), 26 g of ethylene glycol and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Example 18>
Addition of 160 g of 4,4′-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500 ml stirring device and a temperature control device 410 g of product (A-8), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Comparative Example 11>
Addition of 3,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) 103g, alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500ml stirrer and temperature controller 410 g of product (N-1), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Comparative Example 12>
Addition of 160 g of 4,4′-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500 ml stirring device and a temperature control device 410 g of product (N-2), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Comparative Example 13>
Addition of 3,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) 103g, alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500ml stirrer and temperature controller 410 g of product (N-3), 26 g of ethylene glycol, and 1390 g of dimethylformamide were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

<Comparative example 14>
Addition of 160 g of 4,4′-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and alkylene oxide obtained in Example 3 to a four-necked flask equipped with a 2500 ml stirring device and a temperature control device Product (N-4) 410 g, ethylene glycol 26 g, and dimethylformamide 1390 g were charged and reacted at 70 ° C. until the reaction rate (consumption rate) of isocyanate reached 100%. After extending the obtained polyurethane resin solution on a glass plate, the polyurethane resin was obtained by heating at −0.1 MPa (gauge pressure) and 60 ° C. for 6 hours.

  Table 3 shows the physical properties of the polyurethane elastomers obtained in Examples 15 to 18 and Comparative Examples 11 to 14.

  From the results of Table 3, it can be seen that the elastomers of Examples 15 and 16 have improved mechanical strength (particularly, tensile strength at break and elongation at break) as compared with those of Comparative Examples 11 and 13. Similarly, it can be seen that the elastomers of Examples 17 and 18 are improved in mechanical strength (particularly, tensile strength at break and elongation at break) as compared with those of Comparative Examples 12 and 14.

  According to the method for producing an alkylene oxide adduct of the present invention, a post-treatment step for removing a low-boiling volatile component is not required, thereby improving production efficiency and improving the number average functional group number of the alkylene oxide adduct. The resulting alkylene oxide adduct is particularly useful as a raw material for polyurethane resins (including polyurethane foam) obtained by reacting with polyisocyanates.

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Adsorption tower 3 Distillation tower 4 Raw material supply line 5 Removal line 6 Feeding line 7 Volatilizer 8 Recovery line 82 Recovery line 2
9 Tower top line 10 Recovery tank 11 Recovery liquid feed line 12 By-product low boiling point extraction line 13 Circulation line 14 Reaction tower 15 Moisture adsorption tower

Claims (3)

The presence of a Lewis acid catalyst (a), and be Oite the reaction of adding an alkylene oxide (d) the active hydrogen-containing compound (c), it added dividedly 2 to 100 times (d) is reacted, From the reaction mixture (e) consisting of the liquid phase or consisting of the liquid phase and the gas phase, the by-product low-boiling compound (b) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa is intermittently used in an apparatus separate from the reaction vessel. A process for producing an alkylene oxide adduct comprising a step of repeatedly removing the alkylene oxide . The production method according to claim 1, wherein the content of the by-product low-boiling compound (b) in the reaction mixture (e) is 10% by weight or less based on the weight of (e). In the method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component with an organic polyisocyanate (C), alkylene obtained by the production method according to claim 1 or 2 as at least a part of the polyol component A method for producing a foamed or non-foamed polyurethane resin using an oxide adduct.

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