JP2007021435A - Alkoxylation catalyst and method for producing alkoxylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkoxylation catalyst which is prepared from general-purpose raw materials and used for producing an alkoxylate having a narrow distribution of alkylene oxide-added moles. <P>SOLUTION: The alkoxylation catalyst is obtained by mixing component (A) consisting of the organic sulfonate shown by chemical formula (1) (wherein R is a 1-20C alkyl or alkenyl group; x=0-5) with zinc oxide (component (B)) in one or more liquids selected from water, alcohols, glycol ethers and aromatic solvents by 5/1 to 1/10 molar ratio of component (A) to component (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an alkoxylation catalyst and a method for producing an alkoxylate using the catalyst.

  Conventionally, when an alkoxylate is produced commercially by adding an alkylene oxide to an active hydrogen-containing compound such as alcohols and alkylphenols, it is advantageous in terms of versatility, handling, reaction rate, amount of by-products, cost, etc. For this reason, alkali catalysts such as potassium hydroxide and sodium hydroxide are used as alkoxylation catalysts.

  As an alkoxylation catalyst, various acid catalysts and basic catalysts have been developed, but some problems remain in terms of versatility, handling, reaction rate, catalyst removal, by-product amount, and cost of the catalyst. ing.

Recently, alkoxylates with a narrow alkylene oxide addition molar distribution have been reported to have many advantages over conventional alkoxylates with a broad distribution, giving alkoxylates with this narrow alkylene oxide addition molar distribution. Technology relating to the catalyst for oxidization, for example, activation of firing of magnesium oxide and magnesium hydroxide containing magnesium and a metal selected from the group 2B, 4A, 4B, etc. A large number of Al · Mg composite oxide catalysts obtained in this way are disclosed. (For example, Patent Documents 1 to 3)
JP-A-7-227540 JP-A-8-268919 JP-A-10-158384

  However, these alkoxylation catalysts that give alkoxylates having a narrow alkylene oxide addition molar distribution are also not sufficiently narrow to exhibit the originally desired characteristics, and in addition, the instability of the catalyst Therefore, there is a problem that the handling is not simple or the preparation is difficult and the catalyst cost is high. In addition, there are cases where the problem of corrosiveness to metals caused by the catalyst, such as reactors and pipes, and toxicity to human bodies cannot be solved. In addition, various problems such as product odor problems due to unreacted raw materials remaining in the products, generation problems of by-products such as dioxane, dioxolane, polyalkylene glycol, and coloring problems on products cannot be solved. It is in.

  The present invention has been made in view of the above circumstances, and the purpose of the present invention is to prepare an alkoxylation catalyst from a general-purpose raw material, and its operation is extremely easy, and the stability of the preparation operation and handling. For alkoxylation that is high in price, inexpensive, shows a narrow molar distribution of alkylene oxide addition, greatly reduces toxic by-products, and does not deteriorate the appearance or handling of the product. The object is to provide a catalyst and a method for producing an alkoxylate.

（式中、置換基Ｒは炭素数が１〜２０の直鎖及び／又は分岐のアルキル基又はアルケニル基である。また、ｘ＝０〜５である。） In order to achieve the above object, the alkoxylation catalyst of the present invention comprises a component (A) composed of an organic sulfonic acid represented by the following general formula (1) and zinc oxide (component (B)) as a component (A). 1 or 2 selected from water or lower alcohols, higher alcohols, glycol ethers, aromatic solvents at a ratio within the range of / component (B) = 5/1 to 1/10 (molar ratio) It consists of the catalyst composition obtained by mixing in the liquid of a seed | species or more.

(In the formula, the substituent R is a linear and / or branched alkyl or alkenyl group having 1 to 20 carbon atoms, and x = 0 to 5).

  Further, the present invention provides a method for producing an alkoxylate by adding an alkylene oxide to an active hydrogen atom-containing compound, wherein the component (A) and the component (B) according to claim 1 are combined with the active hydrogen atom-containing compound. A method for producing an alkoxylate, characterized in that a catalyst composition obtained by mixing in a part or all of the liquid is used in a reaction system as it is, and an alkylene oxide is added to the active hydrogen atom-containing compound. About.

（式中、置換基Ｒ^１、Ｒ^２は炭素数が１〜２０の直鎖及び／又は分岐のアルキル基又はアルケニル基であり、Ｒ^１、Ｒ^２は同一であっても異なってもよい。また、ｎ＝０〜５、ｍ＝０〜５である。） Furthermore, the present invention provides a method for producing an alkoxylate by adding an alkylene oxide to an active hydrogen atom-containing compound, using a catalyst composition containing a compound represented by the following general formula (2), The present invention relates to a method for producing an alkoxylate characterized by subjecting an alkylene oxide to an addition reaction.

(In the formula, the substituents R ¹ and R ² are linear and / or branched alkyl or alkenyl groups having 1 to 20 carbon atoms, and R ¹ and R ² may be the same or different. Also, n = 0 to 5 and m = 0 to 5.)

  The alkoxylation catalyst of the present invention has the following advantages in commercial production over conventional catalysts, particularly alkoxylation catalysts that give narrow distribution alkoxylates, in the following points. Can be manufactured.

  (1) Catalyst preparation is carried out from general-purpose raw materials, and the preparation operation is very easy. Only a predetermined amount of component (A) (organic sulfonic acid) and component (B) (zinc oxide) are stirred and mixed in a solvent. And the preparation operation is safely completed. Moreover, the cost of the catalyst preparation is very low.

  (2) The handling is very simple because of the stability of the catalyst. Further, in the composition and method of use within the limited range of the present invention, the problem of corrosion of the metal of the reactor and its incidental equipment is low, and the irritating and corrosiveness to the skin of the handling operator is low and safe.

  (3) The reaction rate during the production of the alkoxylate is comparable to that of a conventionally used alkali catalyst and can be sufficiently applied to commercial production.

  (4) An alkoxylate having a narrow alkylene oxide addition molar distribution equivalent to or higher than that of the prior art can be obtained.

  (5) By-products that have been problematic in conventional alkoxylation catalysts that give narrow-distributed alkoxylates, for example, the amount of polyalkylene glycol that greatly reduces the amount of dioxane having carcinogenicity and deteriorates the appearance and handling properties of the product. Can be greatly reduced.

  (6) Good product hue.

  (7) The catalyst of the present invention is effective as an alkoxylation catalyst for a wide range of active hydrogen atom-containing compounds, and in particular, linear or branched saturated or unsaturated alcohols having 4 to 22 carbon atoms, alkylphenols, polyols, etc. It can be suitably used as a catalyst for alkoxylation. Moreover, it can use suitably as an effective catalyst for alkoxylation also with respect to the active hydrogen atom containing compound which has a polymerizable functional group.

  (8) In addition, as the alkoxylation catalyst of the present invention, known alkylene oxide reaction operations, reaction conditions, and reactors can be applied.

  The details of the catalyst for alkoxylation of the present invention, the preparation method thereof, and the production method of alkylene oxide are described in detail below.

  The alkoxylation catalyst of the present invention is versatile and inexpensive, and is very easy to prepare, which is obtained by stirring and mixing organic sulfonic acid and metal oxide that do not require special operation in handling within a specific ratio range. In addition, the catalyst composition has good stability and rich catalytic activity.

  That is, the alkoxylation catalyst of the present invention comprises two components of an organic sulfonic acid represented by the following general formula (1) as the component (A) and zinc oxide as the component (B), water or lower alcohols, higher alcohols. , Glycol ethers, and aromatic solvents are obtained by stirring and mixing in one or more liquids.

（式中、置換基Ｒは炭素数が１〜２０の直鎖及び／又は分岐のアルキル基又はアルケニル基である。また、ｘ＝０〜５である。）

(In the formula, the substituent R is a linear and / or branched alkyl or alkenyl group having 1 to 20 carbon atoms, and x = 0 to 5).

  In the above formula (1), the substituent R is a group that has been introduced into the aromatic ring by substitution with a hydrogen atom of the aromatic ring, and the total number of substituents R (x) and the total number of hydrogen atoms is 5.

  In mixing the component (A) and the component (B), a solvent for uniformly dissolving the component (A) in advance is one kind of the solvent for stirring and mixing, that is, the above water or lower alcohols, higher alcohols, It is desirable to select from glycol ethers and aromatic solvents. More preferably, it is desirable to select water as a solvent for uniformly dissolving the component (A) in advance.

  Examples of the lower alcohols include methanol and ethanol. Examples of the higher alcohols include lauryl alcohol having 3 or more carbon atoms, preferably 8 or more, tridecyl alcohol, oxo alcohol having 12 to 15 carbon atoms, carbon number. Is known natural or synthetic alcohols such as Gerve alcohol in the range of 10 to 24, glycol ethers include ethylene glycol dimethyl ether, and aromatic solvents include benzene, xylene, toluene and the like.

  Also, use after increasing the active ingredient concentration of the catalyst composition by removing some or all of the water and solvent species that do not directly participate in the alkoxylation reaction under heating conditions and / or reduced pressure conditions, or have adverse effects You can also

  In the component (A) represented by the general formula (1), the substituent R is preferably an alkyl group having 1 to 6 carbon atoms, and x is 0 for the purpose of improving the catalyst removability after completion of the alkoxylation reaction. ~ 3 is preferred. Specifically, as the component (A), toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, phenol sulfonic acid, dodecylbenzene sulfonic acid and the like can be suitably used, and a mixture thereof may be used.

  In the present invention, the mixing ratio of the component (A) and the component (B) is component (A) / component (B) = 5/1 to 1/10 (molar ratio), preferably (A) / Component (B) = 3/1 to 1/1 (molar ratio), more preferably 2/1 (molar ratio).

  In the production of the alkoxylate, the component (A) and the component (B) are added to a part or all of the liquid of the active hydrogen atom-containing compound that is the starting material for the alkoxylate, and mixed by stirring. ) And the component (B) can be used in the reaction system as they are, and an alkylene oxide can be added to an active hydrogen atom-containing compound to obtain an alkoxylate.

  Examples of the active hydrogen atom-containing compound include alcohols, polyhydric alcohols, phenols, carboxylic acids, amines, and mixtures thereof.

  Examples of alcohols include primary alcohols, secondary alcohols, and arylalkyl alcohols having a saturated or unsaturated linear or branched alkyl group having 2 to 30 carbon atoms. Specifically, n-octanol, n-decanol, n-dodecanol, oleyl alcohol, 2-ethylhexanol, 2-decanol, 2-dodecanol, lauryl alcohol, tridecyl alcohol, and a carbon number in the range of 12 to 15. Known natural and synthetic alcohols such as oxo alcohols and Gerve alcohols having 10 to 24 carbon atoms can be mentioned.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.

  Examples of phenols include phenol, octylphenol, nonylphenol and the like.

  Examples of the carboxylic acids include fatty acids having a saturated or unsaturated linear or branched alkyl group having 1 to 30 carbon atoms. Specific examples include acetic acid, propionic acid, lauric acid, stearic acid, and oleic acid.

  Examples of amines include primary or secondary amines having a saturated or unsaturated alkyl group having 1 to 30 carbon atoms. Specific examples include octylamine, laurylamine, stearylamine, distearylamine and the like.

  Among these active hydrogen atom-containing compounds, primary alcohols and secondary alcohols having a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms are preferable, and 10 carbon atoms are more preferable. -18 linear or branched saturated or unsaturated primary or secondary alcohols and the like.

  The alkylene oxide added to the active hydrogen atom-containing compound may be any alkylene oxide capable of producing an alkoxylate, but preferably has an oxirane ring such as ethylene oxide, propylene oxide, butylene oxide, etc. In addition to those, epoxide species such as α-olefin epoxide are exemplified, and among them, ethylene oxide is preferable.

  Further, in the present invention, a catalyst composition containing a compound represented by the following general formula (2) prepared separately in advance as an essential and main component is added to the reaction system as an alkoxylation catalyst, and An alkoxylate can also be obtained by addition reaction of oxide.

  The compound of the general formula (2) is an organic sulfonic acid represented by the general formula (1) limited in the present invention and a known zinc compound (such as zinc oxide or zinc hydroxide) that can be appropriately selected, such as ethylene glycol dimethyl ether. It can be obtained by stirring and mixing in a dispersing agent and appropriately purifying the stirring mixture.

（式中、置換基Ｒ^１、Ｒ^２は炭素数が１〜２０の直鎖及び又は分岐のアルキル基又はアルケニル基であり、Ｒ^１、Ｒ^２は同一であっても異なるものであってもよい。また、ｎ＝０〜５、ｍ＝０〜５である。）

(In the formula, substituents R ¹ and R ² are linear and / or branched alkyl groups or alkenyl groups having 1 to 20 carbon atoms, and R ¹ and R ² may be the same or different. Also, n = 0 to 5 and m = 0 to 5.)

In the general formula (2), the substituents R ¹ and R ² are preferably alkyl groups having 1 to 5 carbon atoms, and n and m are preferably 0 to 3. More preferably, the compound represented by the general formula (2) is a phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, a neutralization reaction product of cumene sulfonic acid and zinc oxide.

  Using the alkoxylation catalyst of the present invention, a known alkali catalyst such as potassium hydroxide or sodium hydroxide is added to an alkoxylate crude product obtained by adding alkylene oxide to an active hydrogen atom-containing compound by the above operation. An appropriate amount can be additionally added, and a desired amount of alkylene oxide can be further added to the active hydrogen atom-containing compound.

  Next, although the manufacturing method for obtaining an alkoxylate using the catalyst for alkoxylation of this invention is demonstrated, the manufacturing conditions for obtaining the alkoxylate of this invention are not limited to this.

  The amount of the catalyst for alkoxylation in the addition reaction of alkylene oxides of the present invention is 0.01 to 20% by weight (in terms of solid content), more preferably 0.1 to 10% by weight (based on the charged amount of the active hydrogen atom-containing compound). (In terms of solid content).

  As a method for adding the catalyst, a powdery, pelletized, or paste-like alkoxylation catalyst is dispersed in an appropriately selected solvent, and then the catalyst of the present invention is charged into the active hydrogen atom-containing compound in the reactor. by. More preferably, the alkoxylation catalyst of the present invention is added to a part of the active hydrogen atom-containing compound as a reaction raw material, premixed to prepare a catalyst dispersion, and then the dispersion is added to the reaction system. It is desirable.

  The reaction temperature applicable in the present invention is 40 to 240 ° C., and in commercial production, 80 to 180 ° C. is preferable from the viewpoint of reaction rate, removal of reaction heat, side reaction suppression, and product deterioration.

  Reactors that can be used include heating, cooling, depressurization, and pressurization, and a reactor equipped with a raw material inlet, a product outlet, an alkylene oxide and nitrogen inlet tube, a stirrer, a thermometer, and a pressure gauge. Can be suitably used.

  Regarding the preparation of the reaction raw material, usually, a predetermined amount or a part of the active hydrogen atom-containing compound is first charged into the reactor, and then the predetermined amount of the alkoxylation catalyst of the present invention is charged, followed by nitrogen substitution, And dehydration under reduced pressure in the temperature range of 1 to 110 ° C. Next, a predetermined amount of alkylene oxide is introduced under the above reaction temperature conditions, and the addition reaction proceeds.

  If necessary, one or a mixture of two or more alkali catalysts can be added to the reaction system, and a predetermined amount of alkylene oxide can be sequentially introduced and added under known alkylene oxide addition reaction conditions.

  In addition, in the alkylene oxide addition reaction step, it is more preferable that after the introduction of a predetermined amount of alkylene oxide, an operation (aging operation) for continuing the reaction until the pressure decreases and becomes constant.

  A known method can be applied to remove the catalyst after completion of the reaction. Preferably, the alkoxylated catalyst can be removed by subjecting the crude reaction product to a water washing treatment or a filtration treatment. More preferably, the reaction crude product is treated under conditions of addition of water and warming, and then treated with an acid adsorbent and an alkali adsorbent to purify the alkoxylation catalyst of the present invention. When removing a alkoxylation catalyst, when applying a filtration process, it is a more preferable operation to process using a filter aid.

  More preferably, as a method for removing the catalyst, the alkoxylation catalyst of the present invention is a lactic acid equivalent to the neutralization equivalent of the organic sulfonic acid component in the catalyst composition after being subjected to a stirring treatment under water and heating conditions as necessary. A soluble calcium salt such as calcium or calcium citrate is charged into the crude alkoxylate, and after topping under reduced pressure, the resulting precipitate is filtered to remove the residue of the catalyst of the present invention from the crude alkoxylate. Is to remove.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

  A method for preparing the alkoxylation catalyst of the present invention is shown below. In addition, the component (A), the component (B) and the blending ratio (molar ratio) constituting the crude catalyst product, and the solvent or dispersion medium used are as shown in Table 1.

  The reactor that can be used is a separable flask equipped with a stirrer, and, if necessary, a raw material inlet, a product outlet, heating, cooling operation, decompression, pressurization operation, nitrogen introduction pipe, thermometer A reactor equipped with a pressure gauge can be used. In addition, as a simple catalyst preparation method, the alkoxylation catalyst of the present invention can be prepared by using a beaker and a rotor having an appropriate capacity.

[Catalyst preparation method]
Catalyst preparation example (1): p-toluenesulfonic acid (monohydrate) as component (A), zinc oxide as component (B), 93 g of component (A) so as to have a molar ratio of 2: 1, component ( 20 g of B) was weighed. First, 150 g of lauryl alcohol was weighed in a 500 ml beaker, and then 93 g of p-toluenesulfonic acid (monohydrate) weighed was dissolved in 50 g of water, and then stirred in a beaker with a rotor. Added and stirred for 5 minutes. Next, 20 g of the weighed zinc oxide was gradually added to the beaker, and then the stirring was continued for 20 minutes to obtain a dispersed alkoxylation catalyst [1] of the present invention.

  By the same operation as in Catalyst Preparation Example (1), the alkoxylation catalysts [3] to [6] of the present invention and the alkoxylation catalysts [U] to [K] of Comparative Examples were obtained.

  Catalyst preparation example (2): p-toluenesulfonic acid (monohydrate) as component (A), zinc oxide as component (B) in a molar ratio of 1: 5, 20 g of component (A), 43 g of B) was weighed. First, 100 ml of methanol was weighed into a 300 ml separable flask equipped with a stirrer, and then 20 g of the weighed p-toluenesulfonic acid (monohydrate) was dissolved in 10 g of water, followed by stirring. The mixture was added to the separable flask and stirred for 5 minutes. Next, after 43 g of the weighed zinc oxide was gradually added to the separable flask, stirring was continued for 30 minutes to obtain a catalyst composition dispersed in methanol. Next, the obtained catalyst composition was transferred to an evaporator, and methanol and water were removed to obtain a powdery alkoxylation catalyst [2] of the present invention.

  In the same manner as in Catalyst Preparation Example (2), ethylene glycol dimethyl ether was used as a dispersant, and p-toluenesulfonic acid (monohydrate) and zinc oxide were stirred and mixed in a molar ratio of 2: 1. A reaction crude product was obtained, and the reaction crude product was washed with water three times to obtain an alkoxylation catalyst [7] of the present invention represented by the general formula in Table 1.

[Synthesis experiment]
Synthesis experiment (1): Heating, cooling operation, decompression, pressurization operation are possible, and a reactor equipped with a raw material inlet, a product outlet, an alkylene oxide and nitrogen inlet tube, a stirrer, a thermometer, and a pressure gauge Then, 1955 g of lauryl alcohol was charged, and then 85.2 g of the alkoxylation catalyst [1] of the present invention in a dispersed state (catalyst active ingredient 40 g) was charged, followed by nitrogen substitution and dehydration under reduced pressure at a temperature of 110 ° C. . Next, after gradually heating to 140 ° C. and reaching 140 ° C., among 571 g of ethylene oxide (equivalent to 1.2 mol with respect to 1 mol of raw material alcohol), ethylene oxide was charged to 10% of the predetermined amount of ethylene oxide charged. After charging 57 g and starting the reaction, the temperature of the reaction solution was set to 160 ° C., and the remaining ethylene oxide was introduced and reacted. Thereafter, an operation (aging operation) for continuing the reaction until the reaction pressure decreased and became constant. After cooling the reaction crude product to 90 ° C., 50 g of distilled water was added and the mixture was stirred at 90 ° C. for 30 minutes, and then 30 g of filter aid and lactic acid corresponding to the neutralization equivalent of the organic sulfonic acid component in the catalyst composition. After putting calcium into the reaction crude product, topping under reduced pressure was performed, and the produced precipitate was separated by filtration to obtain a target 1.2 ethylene oxide (EO) adduct of lauryl alcohol.

  In the same manner, a synthesis experiment was performed using the alkoxylation catalysts [2], [3] and [7] of the present invention and the alkoxylation catalysts [A] to [K] of Comparative Examples. The results are summarized in Table 2. The alkoxylation catalysts [4] to [6] of the present invention used tridecyl alcohol as a raw material alcohol (active hydrogen atom-containing compound).

＊１：初期触媒活性指数（落圧速度定数Ｋ_１）＝（−Ｉｎ（Ｐｔ／Ｐｉ）／ｍｉｎ）×１０^−４
反応温度＝１６０℃、触媒量＝対アルコール２重量％、Ｐｔ＝t分後の反応圧、Ｐｉ＝初期反応圧
＊２：触媒量は安全確保の為、実用濃度に低減して合成実験を実施、触媒量＝対アルコール０．０５重量％

* 1: Initial catalyst activity index (decrease rate constant K ₁ ) = (− In (Pt / Pi) / min) × 10 ⁻⁴
Reaction temperature = 160 ° C, catalyst amount = 2% by weight of alcohol, Pt = reaction pressure after t minutes, Pi = initial reaction pressure * 2: The catalyst amount was reduced to a practical concentration to ensure safety, and a synthesis experiment was conducted. , Catalyst amount = 0.05% by weight of alcohol

  Synthesis experiment (2): Using the alkoxylation catalyst [1] of the present invention, 2000 g of the 1.2 mol EO adduct of lauryl alcohol obtained in the synthesis experiment (1) was transferred to a reactor, and 0% potassium hydroxide was added. 0.8 g (in terms of solid content) is added, and then purged with nitrogen and dehydrated under reduced pressure at a temperature of 110 ° C. Next, 825 g of ethylene oxide (corresponding to 3.8 mol per mol of raw material alcohol) was gradually introduced at a reaction temperature of 140 ° C. to cause reaction. Thereafter, an operation (aging operation) for continuing the reaction until the reaction pressure decreased and became constant. After the reaction crude product was cooled to 90 ° C., glacial acetic acid equivalent to a neutralization equivalent was added to the reaction crude product to obtain a 5EO adduct of the desired lauryl alcohol.

  Using the alkoxylation catalysts [3] and [7] of the present invention and the alkoxylation catalysts [a], [ki], and [ku] of comparative examples, a synthesis experiment was conducted in the same manner, and EO addition was performed. The odor and hue of the product were evaluated by the following methods. The results are summarized in Table 3.

Odor: The odor was evaluated as follows in comparison with a sensory test based on the catalyst [ki] (potassium hydroxide) of Comparative Example.
○: Equivalent to comparative example [ki] or no irritating odor or unpleasant odor.
Δ: Slightly irritating and unpleasant odor compared to Comparative Example [Ki].
X: Strong irritating odor and unpleasant odor compared to Comparative Example [Ki].

Hue: The appearance was compared visually with the catalyst [K] (potassium hydroxide) of the comparative example, and the hue was evaluated as follows.
○: Has the same or good hue as the comparative example [ki].
Δ: Slightly colored as compared with Comparative Example [K].
X: Remarkably colored as compared with Comparative Example [ki].

＊３：ＥＯ鎖狭分布度：最も含有量（重量％）の多い付加モル体をｎ_ｍａｘとするとき、その前後２モル範囲の含有量（Ｙ）を示す。
＊４：触媒量対アルコール０．０５重量％にて、１段階反応で合成実験を実施した。

* 3: Degree of narrow distribution of EO chain: When the addition molar body having the largest content (% by weight) is n _max , the content (Y) in the range of 2 moles before and after that is shown.
* 4: The synthesis experiment was conducted in a one-step reaction with a catalyst amount of 0.05% by weight of alcohol.

  Synthesis experiment (3): 3 mol equivalent of ethylene to lauryl alcohol was obtained in the same manner as in the synthesis experiment (1) except that the reaction temperature was 180 ° C. using the alkoxylation catalyst [1] of the present invention. Oxide was introduced to obtain the desired 3EO adduct of lauryl alcohol. In addition, using KOH (comparative example [ki]) as a comparative example, a synthesis experiment was performed at a reaction temperature of 180 ° C. and a catalyst amount of 0.03% by weight (vs. crude product). The distribution of the number of moles of ethylene oxide added to the 3EO adduct of lauryl alcohol obtained in the synthesis experiment (3) is shown in FIG.

  As shown in FIG. 1, the alkoxylate by the alkoxylation catalyst of the present invention has a narrow addition mole number distribution of ethylene oxide (EO), and generates little unreacted raw alcohol or by-product (dioxane). There is no odor and the hue is good.

  The alkoxylate produced according to the present invention is useful as a component of a surfactant as a detergent, an emulsifier, a dispersant, and a stabilizer, and is used in various kinds such as cosmetics, detergents, foods, paints, various oils and plasticizers. Can be used for chemical raw materials.

It is a figure which shows EO addition mole number distribution of the ethylene oxide adduct obtained by the synthesis experiment (3).

Claims (3)

Component (A) composed of an organic sulfonic acid represented by the following general formula (1) and zinc oxide (component (B)), component (A) / component (B) = 5/1 to 1/10 (molar ratio) ) And a catalyst composition obtained by mixing in one or more liquids selected from water or lower alcohols, higher alcohols, glycol ethers and aromatic solvents. A catalyst for alkoxylation characterized by the above.

(In the formula, the substituent R is a linear and / or branched alkyl or alkenyl group having 1 to 20 carbon atoms, and x = 0 to 5).   In the method for producing an alkoxylate by adding an alkylene oxide to an active hydrogen atom-containing compound, the component (A) and the component (B) according to claim 1 are mixed with a part or all of the active hydrogen atom-containing compound. A method for producing an alkoxylate, characterized in that a catalyst composition obtained by mixing in an inside is used in a reaction system as it is, and an addition reaction of alkylene oxide is carried out on the active hydrogen atom-containing compound. In a method for producing an alkoxylate by adding an alkylene oxide to an active hydrogen atom-containing compound, a catalyst composition containing a compound represented by the following general formula (2) is used, and an alkylene oxide is added to the active hydrogen atom-containing compound. A method for producing an alkoxylate characterized by the above.

(In the formula, the substituents R ¹ and R ² are linear and / or branched alkyl or alkenyl groups having 1 to 20 carbon atoms, and R ¹ and R ² may be the same or different. Also, n = 0 to 5 and m = 0 to 5.)

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