Method for producing aliphatic alcohol alkylene oxide adduct

Abstract

To provide an aliphatic alcohol alkylene oxide adduct in which the content of dioxane is reduced.SOLUTION: A method for producing an aliphatic alcohol alkylene oxide adduct comprises step A of adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate, wherein, the step A is followed by step B and step C, where the step B is a step of removing perchlorate used in the step A, and the step C is a step of removing dioxane generated in the step A.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an aliphatic alcohol alkylene oxide adduct. [Background technology]

[0002] Aliphatic alcohol alkylene oxide adducts are known as nonionic surfactants with excellent emulsifying and detergency properties. A known method for producing an aliphatic alcohol alkylene oxide adduct is a method in which an alkylene oxide addition step using a perchlorate and an alkylene oxide addition step using an alkali catalyst are carried out consecutively (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-11489 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the aliphatic alcohol alkylene oxide adduct obtained by the method described in Patent Document 1 contains a large amount of dioxane, a reaction by-product, which causes an odor and is also a concern for its effects on the human body, so the uses of the aliphatic alcohol alkylene oxide adduct obtained by the method described in Patent Document 1 have been limited. The present invention provides an aliphatic alcohol alkylene oxide adduct having a low dioxane content. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention provides a method for producing an aliphatic alcohol alkylene oxide adduct, which includes step A of adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate, and further includes steps B and C performed after step A, in which step B is a step of removing the perchlorate used in step A, and step C is a step of removing dioxane produced in step A. [Effects of the Invention]

[0006] According to the present invention, an aliphatic alcohol alkylene oxide adduct having a low dioxane content can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention is a method for producing an aliphatic alcohol alkylene oxide adduct, which comprises step A of adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate. The present invention includes step A and steps B and C which are carried out after step A. Step B is a step for removing the perchlorate used in step A, and step C is a step for removing dioxane produced in step A.

[0008] Step A is a step of adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate (first alkylene oxide addition step). In step A, the perchlorate can function as a reaction catalyst for the ring-opening addition reaction of the alkylene oxide. The perchlorate is preferably a perchlorate of a divalent or trivalent metal, more preferably a perchlorate of a metal selected from Mg, Zn, and Al, and particularly preferably magnesium perchlorate, zinc perchlorate, or aluminum perchlorate. These perchlorates may be used alone or in combination of two or more.

[0009] Examples of the aliphatic alcohol used in step A include monohydric aliphatic alcohols and polyhydric (for example, dihydric to tetrahydric) aliphatic alcohols. Monohydric aliphatic alcohols are preferred from the viewpoint of narrowing the molecular weight distribution.

[0010] Examples of the aliphatic alcohol include aliphatic alcohols having 1 to 24 carbon atoms. The aliphatic alcohol is preferably aliphatic alcohols having 8 to 24 carbon atoms, and more preferably aliphatic alcohols having 12 to 18 carbon atoms. The aliphatic alcohol may be a natural alcohol or a synthetic alcohol (Ziegler alcohol, oxo alcohol, etc.). Furthermore, the aliphatic alcohol may be a single aliphatic alcohol having a specific number of carbon atoms, or a mixture of multiple aliphatic alcohols having 1 to 24 carbon atoms.

[0011] Examples of the aliphatic alcohols having 1 to 24 carbon atoms include saturated aliphatic alcohols having 1 to 24 carbon atoms (methanol, ethanol, n-propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and nonadecyl alcohol), unsaturated aliphatic alcohols having 1 to 24 carbon atoms (propenyl alcohol, butenyl alcohol, 1-pentenyl alcohol, etc.), and the like. alcohol, 1-octenyl alcohol, 1-decenyl alcohol, 1-dodecenyl alcohol, tridecenyl alcohol, pentadecenyl alcohol, oleyl alcohol, gadoleyl alcohol, linoleyl alcohol, etc.), and alicyclic alcohols having 3 to 24 carbon atoms (cyclopropanol, cyclopentanol, cyclohexanol, methylcyclohexyl alcohol, ethylcyclohexyl alcohol, n-propylcyclohexyl alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol, adamantyl alcohol, etc.). The chain hydrocarbon group of the aliphatic alcohol may be linear or branched. The aliphatic alcohol is preferably a primary alcohol or a secondary alcohol, more preferably a primary alcohol. Moreover, the aliphatic alcohol is preferably dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, or a mixture containing at least one of these.

[0012] The first alkylene oxide added to the aliphatic alcohol in step A includes alkylene oxides (hereinafter sometimes abbreviated as "AO") having 2 to 8 carbon atoms (preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms). Examples of AO include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2- or 2,3-butylene oxide, and tetrahydrofuran. Of these, EO and PO are preferred, and EO is more preferred. These alkylene oxides may be used alone or in combination of two or more. When used in combination, the addition may be in the form of a block in which the same structural unit is added in succession, or in the form of an irregular addition.

[0013] The number of moles of the first AO added to the aliphatic alcohol in step A is not particularly limited, and can be, for example, 1 to 20 moles on average per mole of hydroxyl groups in the aliphatic alcohol. In an embodiment of the production method of the present invention that includes step D (described in detail below) of adding a second alkylene oxide, the average number of moles of the first AO added per mole of hydroxyl groups in the aliphatic alcohol is preferably 1 to 8 moles, and more preferably 1 to 3 moles on average. This range is preferable because step D can be carried out efficiently and the surfactant activity of the aliphatic alcohol alkylene oxide adduct obtained by the production method of the present invention that includes step D is improved. The average number of moles of the first alkylene oxide added per mole of hydroxyl groups in the aliphatic alcohol can be calculated from the weight of the first alkylene oxide used in step A and the hydroxyl value of the aliphatic alcohol.

[0014] Step A is carried out by adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate. A specific example of Step A is a method in which the following steps (a1), (a2), and (a3) ​​are carried out in this order. (a1) A perchlorate and an aliphatic alcohol are placed in a sealable pressure-resistant reaction vessel equipped with a stirrer, and water is removed from the mixture of the perchlorate and the aliphatic alcohol as needed. (a2) Next, a first alkylene oxide is blown into the mixture under normal pressure or increased pressure while stirring, and a ring-opening addition reaction of the alkylene oxide to the hydroxyl group of the aliphatic alcohol is carried out, if necessary, under increased pressure. (a3) Furthermore, if necessary, the pressure in the pressure-resistant reactor is reduced to remove unreacted alkylene oxide.

[0015] In step A, the amount of perchlorate used is preferably 0.001 to 1% by weight, more preferably 0.003 to 0.8% by weight, and particularly preferably 0.005 to 0.5% by weight, based on the total weight of the perchlorate and the aliphatic alcohol, from the viewpoint of reaction rate and the like.

[0016] The dehydration of the mixture of perchlorate and aliphatic alcohol, which is carried out as necessary in step A, can be carried out by known methods such as a method of heating to 100° C. or higher or a method of dehydrating under reduced pressure.

[0017] In step A, the temperature conditions for blowing in the first alkylene oxide and carrying out the ring-opening addition reaction of the alkylene oxide to the hydroxyl groups of the aliphatic alcohol are preferably 50 to 150°C, and the reaction time is preferably 2 to 20 hours. When blowing in the alkylene oxide and carrying out the ring-opening addition reaction of the alkylene oxide are carried out under pressure, the pressure is preferably 0.1 to 0.6 MPa.

[0018] In step A, an acid catalyst can be used as a reaction catalyst for the ring-opening addition reaction of alkylene oxide. Preferred examples of the acid catalyst include Lewis acid catalysts (such as tin tetrachloride, antimony pentachloride, iron trichloride, and boron trifluoride) and protonic acid catalysts [sulfuric acid (salts), phosphoric acid (salts), and nitric acid (salts)]. When the protonic acid catalyst is a salt of a protonic acid, salts other than those of alkali metals are preferred, and salts of divalent or trivalent metals (e.g., Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, and Al, preferably Mg, Zn, Ca, Sr, Ba, and Al, and more preferably Mg, Zn, and Al) are even more preferred.

[0019] The acid catalyst is preferably one containing at least one selected from the group consisting of Lewis acid, sulfuric acid (salt), phosphoric acid (salt), and nitric acid (salt). In this specification, acid (salt) means an acid and / or an acid salt.

[0020] When a perchlorate and an acid catalyst are used in combination, the amount of the acid catalyst used in step A is preferably 0.001 to 1% by weight, more preferably 0.003 to 0.8% by weight, and particularly preferably 0.005 to 0.5% by weight, based on the total weight of the perchlorate, the acid catalyst, and the aliphatic alcohol, from the viewpoint of reaction rate and the like.

[0021] The production method of the present invention includes step A followed by steps B and C. Step B is a step of removing the perchlorate used in step A, and step C is a step of removing the dioxane produced in step A. There are no particular limitations on the order in which steps B and C are performed, but it is preferable to perform step B first, from the viewpoint of being able to effectively reduce the amount of dioxane, etc.

[0022] Step B is a step of removing the perchlorate used in step A, and there are no limitations on the method for removing the perchlorate as long as it can be done. Among these, it is preferable to include an adsorbent mixing step (step B1, adsorbent mixing step) of adding an adsorbent that adsorbs perchlorate used in step A to obtain a mixture of the adsorbent and the reaction mixture obtained in step A, and a step (step B2, solid-liquid separation step) of removing solid components from the mixture of the adsorbent and the reaction mixture to obtain an alkylene oxide adduct.

[0023] The reaction mixture obtained in step A is a mixture obtained after blowing a first alkylene oxide into a mixture of perchlorate and aliphatic alcohol to carry out a ring-opening addition reaction of the alkylene oxide. The mixture contains perchlorate, perchlorate residues (including decomposition products of the perchlorate), the first alkylene oxide adduct of the aliphatic alcohol, by-products such as dioxane, an optional acid catalyst, and acid catalyst residues (including decomposition products of the acid catalyst). The adsorbent adsorbs perchlorate, perchlorate residues (including decomposition products of the perchlorate), an optional acid catalyst, and acid catalyst residues (including decomposition products of the acid catalyst).

[0024] When step B includes step B1, a known inorganic adsorbent can be used as the adsorbent added in step B1. The adsorbent refers to a compound capable of adsorbing specific metals or ions by physical or electrostatic adsorption. Preferred adsorbents include inorganic compounds containing as their main components oxides and / or hydroxides of Group 2 metals, oxides and / or hydroxides of Group 13 metals, and oxides and / or hydroxides of Group 14 metals in the periodic table. Specific examples include magnesium oxide, magnesium silicate, aluminum oxide, aluminum silicate, alumina magnesia (a solid solution of MgO and Al2O3), hydrotalcite, activated clay, and acid clay. Of these, hydrotalcite is more preferred.

[0025] The adsorbent preferably has a volume average particle size of 50 to 500 μm from the viewpoints of ease of handling and the efficiency of the solid-liquid separation step carried out after the adsorbent mixing step.

[0026] The adsorbent may be a commercially available product, such as the Kyoward series (Kyoward is a registered trademark of Kyowa Chemical Industry Co., Ltd.) and the Zeolum series (Zeolum is a registered trademark of Tosoh Corporation).

[0027] The amount of adsorbent added is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight, based on the total weight of the reaction mixture obtained in step A.

[0028] There are no limitations on the method for adding the adsorbent to the reaction mixture; the adsorbent may be added while stirring the reaction mixture, or may be added without stirring. Furthermore, water may be added to the reaction mixture during or after the addition, or both during and after the addition. From the viewpoint of the efficiency of the subsequent step B2, the amount of water added is preferably 0.1 to 10 wt %, more preferably 0.1 to 6 wt %, and particularly preferably 0.5 to 2 wt %, based on the total weight of the reaction mixture.

[0029] In step B1, it is preferable to further stir the reaction mixture after adding the inorganic adsorbent, and when stirring the reaction mixture after adding the inorganic adsorbent, it is more preferable to stir the mixture while heating it to 60 to 100° C. The stirring time after adding the inorganic adsorbent to the reaction mixture is preferably 0.5 to 2 hours.

[0030] In the production method of the present invention, if necessary, dehydration from the mixture of the adsorbent and the reaction mixture may be carried out after step B1 and before step B2. Dehydration may be carried out by reducing the pressure while heating and stirring the mixture (reduced-pressure dehydration). When dehydration is carried out under reduced pressure, it is preferably carried out at a temperature of 50 to 160°C (more preferably 90 to 120°C) and at an absolute pressure of 130 to 66,000 Pa (more preferably 600 to 6,600 Pa). The reduced-pressure dehydration time is preferably 0.5 to 6 hours.

[0031] When the production method of the present invention includes step B2 (solid-liquid separation step), removal of solid components from the mixture of the adsorbent and the reaction mixture may be carried out using a known filter (such as a Kiriyama funnel, a Buchner funnel, a Nutsche filter, a filter press, or a sparkler filter). The filtration may be carried out under normal pressure, reduced pressure, or increased pressure as necessary, and by filtering the mixture of the adsorbent and the reaction mixture, solid components can be removed, thereby obtaining an alkylene oxide adduct precursor as a liquid component.

[0032] Step C is a step for removing the dioxane produced in Step A. The dioxane removal step can be carried out by heating the product obtained in the previous step, bubbling an inert gas (such as nitrogen gas) through the liquid under reduced pressure, adding water or steam to a solution heated above the boiling point of water and then distilling off the vaporized water, or by extraction and separation using a solvent such as water by a known method. Note that "under reduced pressure" means "under pressure conditions lower than normal pressure." Since dioxane has a boiling point of 101°C at atmospheric pressure, it can be removed by heating it above its boiling point under atmospheric pressure or reduced pressure. Furthermore, since dioxane volatilizes into the gas phase, it can be removed from a liquid by bubbling an inert gas into the liquid under reduced pressure. Furthermore, since dioxane is soluble in water, it can be removed by extraction and separation using water. The heat treatment may be carried out, for example, by heating the reaction mixture obtained in the previous step at a temperature of 100° C. to 160° C. for 0.5 to 2 hours. Examples of the bubbling method include a method in which nitrogen gas is bubbled into the reaction mixture obtained in the previous step under reduced pressure at a temperature of 100°C to 160°C. From the viewpoint of effectively reducing the dioxane content, a method in which water is added to the reaction mixture obtained in the previous step and then heat-treated, and a method in which nitrogen gas is bubbled into the reaction mixture under reduced pressure at a temperature of 100°C to 160°C are preferred. The bubbling pressure is preferably adjusted to a constant pressure using a pressure regulator, preferably 20 to 100 mmHg (2666.45 Pa to 13332.25 Pa). The amount of bubbling nitrogen gas is preferably 0.1 liter / minute to 1 liter / minute.

[0033] The production method of the present invention may further include a step of further adding a second alkylene oxide (step D). Step D is a step carried out after step A, and specifically, step D is a step of further adding a second alkylene oxide to the first alkylene oxide adduct of an aliphatic alcohol obtained after carrying out step A. From the viewpoint of reducing the dioxane concentration in the final product and achieving excellent work efficiency, step D is preferably performed after step A and steps B and C subsequent to step A, and more preferably after step A, step B, and step C are performed in this order.

[0034] The second alkylene oxide used in step D may be the same as the first alkylene oxide exemplified in step A, and the preferred examples are also the same. The first alkylene oxide and the second alkylene oxide are preferably different, but may be the same. The second alkylene oxide (AO) may be used alone or in combination of two or more. When two or more types are used in combination, the addition method may be a method in which the same structural units are added in consecutive blocks, or a method in which they are added irregularly.

[0035] The number of moles of the second alkylene oxide added is not particularly limited, but is preferably 1 to 80 moles on average, and more preferably 1 to 40 moles on average, per mole of hydroxyl groups in the aliphatic alcohol. This range is preferred because the surfactant activity of the resulting aliphatic alcohol alkylene oxide adduct is improved. The average number of moles of the second alkylene oxide added per mole of hydroxyl groups in the aliphatic alcohol can be calculated from the weight of the second alkylene oxide used in step D and the hydroxyl value of the first AO adduct of the aliphatic alcohol.

[0036] Step D is preferably carried out in the presence of an alkali catalyst. The alkali catalyst is added after step A is carried out to obtain the first AO adduct of an aliphatic alcohol and before step D is carried out. In this specification, the step of adding the alkali catalyst is referred to as the "alkali catalyst addition step," and the "alkali catalyst addition step" of adding the alkali catalyst used in step D is distinguished as a step separate from step D.

[0037] Step B and / or Step C may be performed before the alkali catalyst addition step. Alternatively, Step C (dioxane removal step) may be performed after the alkali catalyst addition step and before Step D, or Step C may be performed before the alkali catalyst addition step. Alternatively, Step C may be performed before the alkali catalyst addition step and after the alkali catalyst addition step. By carrying out step C before carrying out step D, not only the dioxane produced in step A but also water that causes a side reaction of the alkylene oxide reacted in step D is removed, and the reaction rate of the alkylene oxide is preferably increased. In particular, it is more preferable to carry out step C after the alkali catalyst addition step and before carrying out step D.

[0038] When step C is carried out before step D, it is preferable to carry out the step C by a method of heat treatment and a method of bubbling an inert gas into the liquid under reduced pressure.

[0039] Preferred examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, etc. The amount of the alkali catalyst used is preferably 0.0001 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the weight of the first AO adduct of an aliphatic alcohol.

[0040] Step D is carried out by adding a second alkylene oxide to the first AO adduct of an aliphatic alcohol in the presence of the alkali catalyst added in the "alkali catalyst addition step." Step D can be carried out using a pressure-resistant reaction vessel similar to that used in step A. Step D can be carried out by placing the material obtained in the step immediately preceding step (including the first AO adduct of an aliphatic alcohol) and the alkali catalyst in the reaction vessel, dehydrating the mixture as necessary in the same manner as in step A, and then blowing in an alkylene oxide under normal pressure or increased pressure while stirring. In step D, the ring-opening addition reaction of the second AO to the hydroxyl group of the first AO adduct of the aliphatic alcohol may be carried out under pressure as needed, and further, the pressure in the pressure-resistant reaction vessel may be reduced to remove unreacted alkylene oxide as needed.

[0041] The reaction temperature in step D is preferably 50 to 150°C, and the reaction time is preferably 2 to 20 hours. When the blowing of alkylene oxide and the ring-opening addition reaction of alkylene oxide are carried out under pressure as needed, the pressure is preferably 0.1 to 0.6 MPa. Dehydration, which is carried out as needed, can be carried out by known methods such as a method of heating to 100°C or higher and a method of dehydration under reduced pressure.

[0042] In the production method of the present invention, it is preferable to carry out an alkali catalyst removal step of removing the alkali catalyst after step D. The alkali catalyst removal step can be carried out by a method of neutralizing the alkali catalyst with an acid (acetic acid or the like), or by a method of adsorbing the alkali catalyst onto an adsorbent such as those exemplified in the adsorbent mixing step, followed by carrying out a known solid-liquid separation method such as filtration. Of these, the method of adsorbing the alkali catalyst onto an adsorbent and then separating the adsorbent is preferred.

[0043] As the adsorbent used in the alkali catalyst removal step, known solid acids can be preferably used, and examples thereof include inorganic metal solids (activated alumina, zirconia sulfate, metal phosphates, aluminum dihydrogen triphosphate, titanium oxide, silica-titania composite oxide, silica-calcium oxide composite oxide, silica-magnesia composite oxide, zeolite, etc.) and cation exchange resins.

[0044] Among the solid acids, the inorganic metal solids that can be used include those available on the market such as the Kyoward series and Zeorum series.

[0045] The alkali catalyst removal step using a solid acid can be carried out by the same operations as in the adsorbent mixing step and the solid-liquid separation step, except that the adsorbent is changed to a solid acid.

[0046] In addition to the method using a solid acid, the alkali catalyst removal step can also be performed by a method in which the catalyst is neutralized with a liquid acid (hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, etc.) and the resulting salt is removed by filtration; a method in which the catalyst is dissolved in a solvent (methanol, etc.) and washed with water to remove the alkali catalyst dissolved in water; a method in which the alkali catalyst is adsorbed and removed using an ion exchange resin; and a method in which the catalyst is neutralized with carbon dioxide gas and the resulting carbonate is filtered, etc.

[0047] When the alkali catalyst removal step is carried out by washing with water, it is preferable to further carry out dehydration. The dehydration is preferably carried out under reduced pressure as needed, while heating (preferably heating to 100 to 150°C). The water content of the aliphatic alcohol alkylene oxide adduct obtained after dehydration is preferably 0.1% by weight or less.

[0048] The aliphatic alcohol alkylene oxide adducts obtained by the production method of the present invention exhibit excellent emulsifying and detergency properties and can be used as solubilizers, emulsifiers, dispersants, detergents, antifoaming agents, antistatic agents, antifogging agents, antifouling agents, antibacterial agents, metal rust inhibitors, lubricants, wetting agents, penetrating agents, resin plasticizers, etc. Furthermore, because the aliphatic alcohol alkylene oxide adducts obtained by the production method of the present invention have a low dioxane content, these agents can be suitably used in foods, cosmetics, pharmaceuticals, detergents, toiletries, agricultural chemicals, inks, textile products, paper products, etc. [Example]

[0049] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the gist of the present invention. Unless otherwise specified, parts mean parts by weight and % means % by weight.

[0050] [Method for measuring dioxane content] The dioxane content in the alkylene oxide adducts of aliphatic alcohols obtained in the Examples and Comparative Examples was measured by gas chromatography (GC measurement) using the headspace method, and the dioxane content in the measurement sample was determined by the calibration curve method. The results are shown in Table 1. The detection limit for dioxane using this measurement method under these conditions is 2 ppm. The measuring device and conditions for the gas chromatography method are as follows: <Apparatus and measurement conditions> Equipment product name: GC-17A (manufactured by Shimadzu Corporation) Column: Product name DB-1 (manufactured by J&W) Size: 0.32mm x 30m Film thickness: 3.0 μm Split ratio: 20:1 Detector: FID Column temperature: 40°C (hold 5 min) → 180°C (hold 5 min) Heating rate: 5℃ / min Inlet temperature: 200℃ Detector temperature: 250℃ Injection volume: 20 microliters (μL) Quantitation: Aqueous solutions of dioxane with concentrations of 2, 10, and 20 ppm were used as the calibration curve.

[0051] [Example 1] (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen. After that, dehydration was carried out under reduced pressure (approximately 20 mmHg, 2666.45 Pa) at 120°C for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). In step C, the product obtained after step B was heated at 110°C for 1 hour to remove dioxane and the water added in the inorganic adsorbent mixing step, thereby obtaining the aliphatic alcohol alkylene oxide adduct (A-1) of Example 1. The dioxane content of (A-1) was measured by the above-mentioned measurement method and was found to be 300 ppm.

[0052] [Example 2] (Addition of the first alkylene oxide) 186 parts (1 mole) of dodecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out under reduced pressure (approximately 20 mmHg, 2666.45 Pa) at 120°C for 1 hour. Then, 44 parts (1 mole) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced for 3 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). In step C, the product obtained after step B was heat-treated at 150°C for 1 hour to remove dioxane and the water added in the inorganic adsorbent mixing step, thereby obtaining the aliphatic alcohol alkylene oxide adduct (A-2) of Example 2. The dioxane content of (A-2) was measured by the above-mentioned measurement method and was found to be 200 ppm.

[0053] [Example 3] (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen. After that, dehydration was carried out under reduced pressure (approximately 20 mmHg, 2666.45 Pa) at 120°C for 1 hour. Then, 132 parts (3 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2The first alkylene oxide addition step (step A) was carried out by introducing the alkylene oxide for 8 hours so as to maintain a pressure of 98 to 294 kPa. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). The product obtained after carrying out step B was heated to 150°C, and then 1 wt% of water based on the weight of the product obtained after carrying out step B was added. Heating was continued for 1 hour to remove dioxane and the added water (step C), thereby obtaining a first alkylene oxide adduct of an aliphatic alcohol (a3). (Addition of a second alkylene oxide) 350 parts of the first alkylene oxide adduct of aliphatic alcohol (a3) ​​and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step, and then the mixture system was purged with nitrogen, and the mixture was heated at 130°C for 1 hour under reduced pressure (approximately 20 mmHg, 2666.45 Pa) to remove the remaining dioxane, and step C after the alkali catalyst addition step was carried out. Next, 220 parts (5 moles) of EO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced so that the pressure became (98 to 294 kPa), and heating and stirring were continued until pressure equilibrium was confirmed, whereby the second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80°C and neutralized by adding 0.3 parts of acetic acid (neutralization step) to remove the alkali catalyst, thereby obtaining an aliphatic alcohol alkylene oxide adduct (A-3). The dioxane content of (A-3) was measured by the above-mentioned measurement method and was found to be 5 ppm.

[0054] [Example 4] (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). The product obtained after step B was heated to 110°C and treated with bubbling nitrogen gas under reduced pressure (approximately 50 mmHg, 6666.1 Pa) for 1 hour to remove dioxane and the water added in the inorganic adsorbent mixing step (step C), thereby obtaining the first alkylene oxide adduct of aliphatic alcohol (a4). The flow rate of nitrogen gas was 0.5 L / min. (Addition of a second alkylene oxide) 306 parts of the first alkylene oxide adduct of aliphatic alcohol (a4) and 0.3 parts of sodium hydroxide were charged into an autoclave to carry out an alkali catalyst addition step, and then nitrogen gas was flowed into the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the atmosphere in the mixed system with nitrogen. Next, 116 parts (2 moles) of PO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2The mixture was introduced so that the pressure became (98 to 294 kPa), and heating and stirring were continued until pressure equilibrium was confirmed, whereby the second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80°C and neutralized by adding 0.3 parts of acetic acid (neutralization step) to remove the alkali catalyst, thereby obtaining an aliphatic alcohol alkylene oxide adduct (A-4). The dioxane content of (A-4) was measured by the above-mentioned measurement method and was found to be 10 ppm.

[0055] [Example 5] (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). Water was added to the product obtained after step B and separated to remove dioxane (step C), thereby obtaining a first alkylene oxide adduct of aliphatic alcohol (a5). The separation was carried out by adding and mixing water so that the weight ratio (W1:Ww) of the product obtained after step B (W1) to water (Ww) was 7:3, allowing the mixture to stand until it separated into two layers, and then removing the water from the lower layer. (Addition of a second alkylene oxide) 306 parts of the first alkylene oxide adduct of aliphatic alcohol (a5) and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step, and then nitrogen gas was passed through the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the atmosphere in the mixed system with nitrogen. Next, 116 parts (2 moles) of PO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 (98 to 294 kPa), and continue heating and stirring until pressure equilibrium is confirmed. After that, 220 parts (5 moles) of EO are added at 160°C until the gauge pressure reaches 1 to 3 kgf / cm. 2 The mixture was introduced so that the pressure became equal to (98 to 294 kPa), and heating and stirring were continued until pressure equilibrium was confirmed again, whereby a second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80°C and neutralized by adding 0.3 parts of acetic acid (neutralization step) to remove the alkali catalyst, thereby obtaining an aliphatic alcohol alkylene oxide adduct (A-5). The dioxane content of (A-5) was measured by the above-mentioned measurement method and was found to be 400 ppm.

[0056] [Example 6] (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby carrying out a solid-liquid separation step (step B2), whereby the solid was removed and the liquid was recovered (step B). The recovered liquid contains the first alkylene oxide adduct of the aliphatic alcohol (a6) and the water added in the inorganic adsorbent mixing step. (Addition of a second alkylene oxide) 306 parts of the liquid containing (a6) and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step, and then nitrogen gas was passed through the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the inside of the mixed system with nitrogen. Subsequently, the mixture was heated at 130°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour to remove the remaining dioxane and the water added in the inorganic adsorbent mixing step, thereby carrying out step C. Next, 116 parts (2 moles) of PO and 220 parts (5 moles) of EO were mixed at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced so as to achieve a pressure of 98 to 294 kPa, and the second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80 ° C., and 3 parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)) and 1 part of water were added. The mixture was stirred at 90 ° C. for 1 hour, then the temperature was adjusted to 60 ° C. and the mixture was subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel and a suction bottle equipped with No. 4 hard filter paper. This performed a solid-liquid separation process to remove the alkali catalyst. The mixture was then dehydrated under reduced pressure (approximately 20 mmHg) at 120 ° C. for 1 hour to obtain the aliphatic alcohol alkylene oxide adduct (A-6). The dioxane content of (A-6) was measured using the above-mentioned measurement method and was found to be 100 ppm.

[0057] [Example 7] (Addition of the first alkylene oxide) The same procedure as in "Addition of first alkylene oxide" in Example 6 was carried out to obtain a liquid containing the first alkylene oxide adduct of aliphatic alcohol (a6) and the water added in the inorganic adsorbent mixing step. (Addition of a second alkylene oxide) 306 parts of the liquid containing (a6) and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step. Furthermore, nitrogen gas was passed through the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the atmosphere in the mixed system with nitrogen. Next, nitrogen gas was bubbled through the mixture for 1 hour at 150°C under reduced pressure (approximately 50 mmHg, 6666.1 Pa) to remove the remaining dioxane and the water added in the inorganic adsorbent mixing step, thereby carrying out step C. The flow rate of the nitrogen gas was 0.5 L / min. Next, 220 parts (5 moles) of EO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced so as to achieve a pressure of 98 to 294 kPa, and the second alkylene oxide addition step was carried out (step D). After confirming the pressure equilibrium, the mixture was cooled to 80°C and neutralized by adding 0.3% acetic acid (neutralization step) to remove the alkali catalyst, thereby obtaining an aliphatic alcohol alkylene oxide adduct (A-7). The dioxane content of (A-7) was measured by the above-mentioned measurement method and was found to be 10 ppm.

[0058] [Example 8] (Addition of the first alkylene oxide) The same procedure as in "Addition of first alkylene oxide" in Example 6 was carried out to obtain a liquid containing the first alkylene oxide adduct of aliphatic alcohol (a6) and the water added in the inorganic adsorbent mixing step. (Addition of a second alkylene oxide) 306 parts of the liquid containing (a6) and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step. Furthermore, nitrogen gas was passed through the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the atmosphere in the mixed system with nitrogen. Next, the mixture was heated to 150°C, water was added, and nitrogen gas was bubbled through for 1 hour under reduced pressure (approximately 50 mmHg, 6666.1 Pa) to distill off the vaporized water, and the remaining dioxane and the water added in the inorganic adsorbent mixing step were removed to carry out step C. The flow rate of nitrogen gas was 0.5 L / min. Next, 290 parts (5 moles) of PO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced so as to achieve a pressure of 98 to 294 kPa, and the second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80°C, and 0.3 parts of acetic acid was added to neutralize the mixture (neutralization step), thereby carrying out the alkali catalyst addition step to obtain an aliphatic alcohol alkylene oxide adduct (A-8). The dioxane content of (A-8) was measured by the above-mentioned measurement method and was found to be 5 ppm.

[0059] Comparative Example 1: Method without performing step C (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to 60°C and subjected to suction filtration under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel equipped with No. 4 hard filter paper and a suction bottle to perform the solid-liquid separation step (step B2). The solid was removed, and the liquid was recovered. The aliphatic alcohol alkylene oxide adduct (A'-1) was obtained by dehydration at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. The dioxane content of (A'-1) was measured using the above-mentioned measurement method and was found to be 2300 ppm.

[0060] Comparative Example 2: Method without performing step C (Addition of the first alkylene oxide) 218 parts (1 mole) of tetradecanol as an aliphatic alcohol and 0.1 parts of aluminum perchlorate were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and the mixture was purged with nitrogen, after which dehydration was carried out at 120°C under reduced pressure (approximately 20 mmHg, 2666.45 Pa) for 1 hour. Next, 88 parts (2 moles) of EO was added at 95°C under a gauge pressure of 1 to 3 kgf / cm 2 The mixture was introduced for 5 hours so as to maintain a pressure of 98 to 294 kPa, and the first alkylene oxide addition step (step A) was carried out. Three parts of synthetic hydrotalcite (product name: Kyoward 500 (Kyowa Chemical Industry Co., Ltd.)), which is an inorganic adsorbent, and one part of water were added to the reaction mixture obtained in step A, and the mixture was stirred at 90°C for one hour to carry out step B1, the inorganic adsorbent mixing step. The mixture of the reaction mixture and inorganic adsorbent obtained in the inorganic adsorbent mixing step was adjusted to a temperature of 60°C, and a solid-liquid separation step was carried out by suction filtering under reduced pressure (approximately 20 mmHg, 2666.45 Pa) using a suction filtration apparatus combining a Buchner funnel with No. 4 hard filter paper set in it and a suction bottle, thereby removing the solid and recovering the liquid (step B). (Addition of a second alkylene oxide) The liquid obtained by carrying out step B (containing the first alkylene oxide adduct of the aliphatic alcohol and the water added in the inorganic adsorbent mixing step) and 0.3 parts of potassium hydroxide were charged into an autoclave to carry out the alkali catalyst addition step, and then nitrogen gas was passed through the gas phase of the reaction vessel at room temperature and atmospheric pressure to replace the atmosphere in the mixed system with nitrogen. Next, 290 parts (5 moles) of PO was added at 160°C under a gauge pressure of 1 to 3 kgf / cm 2 After confirming the pressure equilibrium, 220 parts (5 moles) of EO was introduced at 160°C until the gauge pressure reached 1-3 kgf / cm. 2 The mixture was introduced so as to achieve a pressure of 98 to 294 kPa, and the second alkylene oxide addition step was carried out (step D). After confirming pressure equilibrium, the mixture was cooled to 80°C and neutralized by adding 0.3 parts of acetic acid (neutralization step), yielding an aliphatic alcohol alkylene oxide adduct (A'-2). The dioxane content of (A'-2) was measured by the above-mentioned measurement method and was found to be 850 ppm.

[0061] Table 1 shows the materials used in the production methods of the examples and comparative examples, the method of step C, the order of steps, and the dioxane content of the obtained aliphatic alcohol AO adducts. In Table 1, "A," "B," "C," and "D" in the "Order of steps" column mean "Step A," "Step B," "Step C," and "Step D," respectively. In the "Order of steps" column, "Catalyst addition" means the "catalyst addition step" in the second AO addition, "Neutralization" means the "neutralization step" in the second AO addition, and "Solid-liquid separation" means the "solid-liquid separation step" in the second AO addition.

[0062] [Table 1]

[0063] As shown in Table 1, the aliphatic alcohol alkylene oxide adduct obtained by the production method of the Example had a significantly lower dioxane content than the aliphatic alcohol alkylene oxide adduct obtained by the production method of the Comparative Example. These results indicate that the aliphatic alcohol alkylene oxide adducts obtained by the production method of the present invention have a low dioxane content, and therefore these agents can be suitably used in foods, cosmetics, pharmaceuticals, detergents, toiletries, pesticides, inks, textile products, paper products, etc.

Claims

1. A method for producing an aliphatic alcohol alkylene oxide adduct, comprising step A of adding a first alkylene oxide to an aliphatic alcohol in the presence of a perchlorate, Step B and step C are performed after step A, Step B is a step of removing the perchlorate used in Step A, In the method for producing an aliphatic alcohol alkylene oxide adduct, step C is a step of removing the dioxane produced in step A.

2. 2. The method for producing an aliphatic alcohol alkylene oxide adduct according to claim 1, wherein step C is a step of bubbling nitrogen gas under reduced pressure at a temperature of 100°C to 160°C.

3. Further comprising step D performed after step A, 3. The method for producing an aliphatic alcohol alkylene oxide adduct according to claim 1 or 2, wherein step D is a step of further adding a second alkylene oxide.

4. The method for producing an aliphatic alcohol alkylene oxide adduct according to claim 3, wherein the step D is carried out after the steps B and C have been carried out.

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