Method for producing aliphatic alcohol ethylene oxide adducts

Abstract

The present invention aims to provide an aliphatic alcohol ethylene oxide adduct with a narrow molecular weight distribution. [Solution] A method for producing an aliphatic alcohol ethylene oxide adduct, comprising a reaction step of introducing ethylene oxide into a reaction vessel containing an aliphatic monoalcohol having 8 to 24 carbon atoms in the presence of a bimetallic cyanide complex, wherein the ratio of the number of moles of ethylene oxide to the number of moles of aliphatic monoalcohol is 2 / 1 to 20 / 1, and the total number of moles of ethylene oxide used in the reaction step, the total number of moles of aliphatic monoalcohol, and the introduction time of ethylene oxide in the reaction step satisfy the following relationship. 1.0 ≥ [(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Time to introduce ethylene oxide (hours)]

Description

[Technical Field]

[0001] The present invention relates to a method for producing an ethylene oxide adduct of an aliphatic alcohol. [Background Art]

[0002] Ethylene oxide adducts of aliphatic alcohols are used, for example, in cosmetics, detergents and the like. As a method for obtaining an ethylene oxide adduct having a narrow molecular weight distribution, a method is known in which polyether monool is obtained by addition polymerization of ethylene oxide in the presence of a double metal cyanide complex catalyst (for example, Patent Document 1).

[0003] However, even the polyether monool obtained by addition polymerization in the presence of a double metal cyanide complex catalyst containing cobalt atoms, zinc atoms and the like described in Example 1 cannot be said to have a sufficiently narrow molecular weight distribution, and there is a demand for a production method capable of producing an ethylene oxide adduct of an aliphatic monoalcohol having a narrower molecular weight distribution. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Unexamined Patent Publication No. 2007-284586 [Summary of the Invention] [Problem to be Solved by the Invention]

[0005] An object of the present invention is to provide an ethylene oxide adduct of an aliphatic alcohol having a narrow molecular weight distribution. [Means for Solving the Problem]

[0006] The present inventors have arrived at the present invention as a result of studies to achieve the above object. In other words, the present invention is a method for producing an aliphatic alcohol ethylene oxide adduct, comprising a reaction step of introducing ethylene oxide into a reaction vessel containing an aliphatic monoalcohol having 8 to 24 carbon atoms in the presence of a bimetallic cyanide complex, wherein the ratio of the number of moles of ethylene oxide to the number of moles of aliphatic monoalcohol is 2 / 1 to 20 / 1, and the total number of moles of ethylene oxide used in the reaction step, the total number of moles of aliphatic monoalcohol, and the introduction time of ethylene oxide in the reaction step satisfy the following relationship. 1.0 ≥ [(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Time to introduce ethylene oxide (hours)] [Effects of the Invention]

[0007] The manufacturing method of the present invention can produce an aliphatic alcohol ethylene oxide adduct with a narrow molecular weight distribution. Furthermore, the aliphatic monoalcohol ethylene oxide adduct obtained by the manufacturing method of the present invention has excellent penetration into substrates such as fibers due to its narrow molecular weight distribution. [Modes for carrying out the invention]

[0008] <Duplex Metallic Cyanide> The bimetallic cyanide complex in the present invention is a compound also called a complex metal cyanide catalyst or DMC catalyst, and is a compound comprising a bimetallic cyanide (also called a complex metal cyanide or bimetallic cyanide) and an organic complex ligand that forms a complex with this bimetallic cyanide. As the bimetallic cyanide complex used in the production method of the present invention, known composite metal cyanide complex catalysts can be used.

[0009] From the viewpoint of reactivity, preferred bimetallic cyanide complexes used in the present invention include complexes in which zinc hexacyanocobaltate, zinc hexacyanoiridiate, zinc hexacyanoferrate, and cobalt hexacyanocobaltate are used as the bimetallic cyanide, and from the viewpoint of reactivity, complexes in which zinc hexacyanocobaltate is used as the bimetallic cyanide are preferred. Examples of organic complex ligands for the bimetallic cyanide complex in the present invention include water-soluble organic compounds having heteroatoms (e.g., oxygen, nitrogen, phosphorus, or sulfur) that can form a complex with the bimetallic cyanide complex. From the viewpoint of reactivity, preferred organic complex ligands include alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof, with water-soluble aliphatic alcohols (ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, and t-butanol, etc.) and ethers (ethylene glycol dimethyl ether, etc.) being preferred.

[0010] <Aliphatic monoalcohols with 8-24 carbon atoms> The aliphatic monoalcohol having 8 to 24 carbon atoms in this invention is a monoalcohol having 8 to 24 carbon atoms (preferably 10 to 16 carbon atoms), and may be a natural alcohol or a synthetic alcohol (such as Ziegler alcohol or oxo alcohol). If the number of carbon atoms is 7 or less, the resulting aliphatic alcohol ethylene oxide adduct does not provide sufficient emulsifying, solubilizing, or cleaning power when used as a surfactant in detergents, etc. If the number of carbon atoms is 25 or more, the crystallization temperature of the aliphatic alcohol ethylene oxide adduct becomes too high, making it difficult to use as a raw material for detergents, etc.

[0011] As for the aliphatic monoalcohol, primary or secondary alcohols are preferred from the viewpoint of coordination, and primary alcohols are more preferred.

[0012] Examples of aliphatic monoalcohols include saturated aliphatic alcohols, unsaturated aliphatic alcohols, and cyclic aliphatic alcohols. The saturated or unsaturated hydrocarbon groups in aliphatic monoalcohols may be linear or branched. Examples of saturated aliphatic alcohols include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and nonadecyl alcohol. Examples of unsaturated aliphatic alcohols include octenyl alcohol, decenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, pentadecenyl alcohol, oleyl alcohol, gadleyl alcohol, and linoleyl alcohol. Examples of cyclic aliphatic alcohols include ethylcyclohexyl alcohol, propylcyclohexyl alcohol, octylcyclohexyl alcohol, nonylcyclohexyl alcohol, and adamantyl alcohol.

[0013] As aliphatic monoalcohols, saturated aliphatic alcohols and unsaturated aliphatic alcohols are preferred from the viewpoint of compatibility, saturated aliphatic alcohols are more preferred, and isodecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, and octadecyl alcohol are particularly preferred.

[0014] <Method for producing aliphatic monoalcohol ethylene oxide adducts> The present invention provides a method for producing an aliphatic alcohol ethylene oxide adduct, comprising a reaction step of introducing ethylene oxide into a reaction vessel containing an aliphatic monoalcohol having 8 to 24 carbon atoms in the presence of a bimetallic cyanide complex.

[0015] In the production method of the present invention, the reaction step is a step of carrying out an addition reaction in which 2 to 20 moles of ethylene oxide is added to 1 mole of an aliphatic monoalcohol having 8 to 24 carbon atoms in the presence of a double metal cyanide complex.

[0016] The amount of ethylene oxide used in the addition reaction in the reaction step is 2 to 20 moles, preferably 2 to 11 moles, per 1 mole of the aliphatic monoalcohol. If the amount is less than 2 moles, the content of unreacted aliphatic monoalcohol in the aliphatic alcohol ethylene oxide adduct obtained by the production method of the present invention increases, which may cause odor.

[0017] The reaction step can be carried out by reacting an aliphatic monoalcohol and ethylene oxide under known conditions, except for the following: using a double metal cyanide complex or the like as a catalyst; using an aliphatic monoalcohol having 8 to 24 carbon atoms; using ethylene oxide to be added; and introducing ethylene oxide into a reaction vessel containing a mixture of the double metal cyanide complex and the aliphatic monoalcohol at a predetermined rate described later.

[0018] For example, the reaction can be carried out by using a pressure-resistant reaction vessel equipped with a dropping device and capable of stirring and temperature control, and introducing ethylene oxide into the reaction vessel at a predetermined rate described later using the dropping device under stirring while heating the pressure-resistant reaction vessel containing the double metal cyanide complex and the aliphatic monoalcohol.

[0019] That is, the production method of the present invention comprises the steps of: charging and mixing a double metal cyanide complex and an aliphatic monoalcohol into a reaction vessel; and introducing ethylene oxide into the reaction vessel in which the double metal cyanide complex and the aliphatic monoalcohol are present.

[0020] The step of charging and mixing a double metal cyanide complex and an aliphatic monoalcohol into a reaction vessel may be carried out by charging the double metal cyanide complex and the aliphatic monoalcohol into the reaction vessel respectively and stirring them. There is no restriction on the order of charging them into the reaction vessel, either one may be charged first, or both may be charged simultaneously. Furthermore, there is no restriction on stirring conditions as long as uniform mixing can be achieved.

[0021] From the perspective of molecular weight distribution and the like, the amount of the double metal cyanide complex used in the reaction step (i.e., the weight of the double metal cyanide complex charged into the reaction vessel) is preferably 0.001 to 0.030% by weight, more preferably 0.001 to 0.025% by weight, and particularly preferably 0.002 to 0.020% by weight, based on the total weight of the aliphatic monoalcohol and ethylene oxide used in the reaction.

[0022] The weight of the aliphatic monoalcohol charged into the reaction vessel is such that the molar ratio of the total moles of ethylene oxide used in the reaction to the aliphatic monoalcohol is 2 / 1 to 20 / 1.

[0023] After the step of charging the double metal cyanide complex and the aliphatic monoalcohol into the reaction vessel, it is preferable to perform a dehydration step from the viewpoint of reducing the moisture content in the reaction vessel and suppressing by-products.

[0024] The dehydration step performed after the step of charging the double metal cyanide complex and the aliphatic monoalcohol into the reaction vessel is a step of reducing moisture in the mixture inside the reaction vessel by using a method of introducing an inert gas (nitrogen, argon, etc.) into the gas phase and / or liquid phase of the reaction vessel, a method of depressurizing the inside of the reaction vessel, or the like. The temperature of the dehydration step is preferably 80 to 140°C, more preferably 90 to 130°C, from the viewpoint of shortening the dehydration time and the like. The dehydration time is preferably 30 to 480 minutes from the viewpoint of suppressing the formation of peroxides.

[0025] After performing the aforementioned dehydration step as necessary, ethylene oxide is introduced into the reaction apparatus using a dropping device under stirring while heating the pressure-resistant reaction vessel containing the double metal cyanide complex and the aliphatic monoalcohol.

[0026] The step of introducing ethylene oxide into the reaction vessel in the presence of a bimetallic cyanide complex can be carried out by dropwise adding the ethylene oxide to the reaction vessel containing a mixture of the bimetallic cyanide complex and an aliphatic monoalcohol using a dropping device attached to the reaction vessel.

[0027] For the dropwise addition of ethylene oxide, a method can be used in which a pressure-resistant container (e.g., a cylinder) filled with ethylene oxide is connected to the reaction vessel, and the discharge flow rate of ethylene oxide (i.e., the rate of introduction into the reaction vessel) is adjusted by a valve provided on the pressure-resistant container, while introducing ethylene oxide into the reaction vessel. In this case, by adjusting the valve opening to control the discharge flow rate, ethylene oxide can be introduced sequentially over a desired introduction time.

[0028] Furthermore, when introducing ethylene oxide, a flow meter may be installed in the introduction line, and the discharge flow rate (introduction rate) may be controlled to be constant based on the flow meter reading while dripping the ethylene oxide. By using a flow meter to maintain a constant introduction rate, it is possible to anticipate that a predetermined amount of ethylene oxide will be introduced within a predetermined introduction time based on the flow rate and the amount of ethylene oxide to be introduced at the start of introduction (for example, that the pressure vessel will be substantially emptied after a predetermined amount of ethylene oxide has been introduced).

[0029] In the manufacturing method of the present invention, the rate at which ethylene oxide is introduced into the reaction vessel is such that the total number of moles of ethylene oxide used in the reaction step, the total number of moles of aliphatic monoalcohols, and the introduction time of ethylene oxide in the reaction step satisfy the following formula. 1.0 ≥ [(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Time to introduce ethylene oxide (hours)]

[0030] In the present invention, there is no lower limit to the value obtained by the above relational formula, but from the viewpoint of economy and other factors, it is preferable that it be 0.5 or higher.

[0031] By ensuring that the time required for introducing ethylene oxide satisfies the above calculation formula, an aliphatic monoalcohol ethylene oxide adduct with a narrow molecular weight distribution can be obtained.

[0032] In the reaction process, the pressure inside the pressure-resistant reaction vessel increases with the introduction of ethylene oxide. Therefore, ethylene oxide is introduced by injecting it under pressure from a dropping device. The introduction time of ethylene oxide can be adjusted by changing the injection pressure, etc. Here, the ethylene oxide introduction time refers to the elapsed time from the start of ethylene oxide introduction (for example, when the valve is opened and the introduction operation begins) to the end of introduction (for example, when the valve is closed and the introduction operation ends), and does not include any temporary interruptions in the introduction process. A temporary introduction stop time refers to the time when, for example, ethylene oxide is introduced by manually adjusting the valve opening, the valve is temporarily closed during the introduction process to measure the weight of the pressure vessel (e.g., cylinder) and check the remaining amount of ethylene oxide in the vessel. After the weight measurement, the pressure vessel is promptly returned to the introduction line and the dripping is resumed. By checking the remaining amount, the valve opening can be adjusted to achieve an appropriate discharge flow rate for the remaining introduction time, thereby optimizing the introduction speed. Furthermore, from the viewpoint of molecular weight distribution, it is preferable to introduce ethylene oxide at the same rate from the start to the end of the introduction process.

[0033] At the end of the introduction process, the valve may be closed when the desired introduction time has elapsed, and the weight of the pressure vessel (e.g., cylinder) may be measured to confirm that a predetermined amount of ethylene oxide has been introduced into the pressure vessel and that the ethylene oxide in the pressure vessel has been substantially consumed (e.g., the pressure vessel is empty).

[0034] After introducing the entire predetermined amount of ethylene oxide into the reaction vessel and carrying out the reaction step, it is preferable to further carry out a maturation step in which stirring and heating are continued at 90 to 180°C for 30 minutes or more. From the viewpoint of further reducing the amount of unreacted ethylene oxide, it is more preferable that the maturation step be 1 hour or more.

[0035] The manufacturing method of the present invention may include a step after the reaction step in which unreacted ethylene oxide is removed by a known method.

[0036] The step of removing unreacted ethylene oxide can be carried out by reducing the pressure inside the reaction vessel for at least one hour under conditions of 20 to 180°C and -0.1 to 0 MPa (gauge pressure).

[0037] The manufacturing method of the present invention may also include a step after the reaction step to remove the bimetallic cyanide complex used as a catalyst, such as the method described as a filtration step in Japanese Patent Publication No. 7079304.

[0038] The manufacturing method of the present invention may further include a step of adding a known antioxidant to the aliphatic monoalcohol ethylene oxide adduct obtained by the above-mentioned step in order to ensure stability during storage.

[0039] The molecular weight distribution (Mw / Mn) of the aliphatic monoalcohol ethylene oxide adduct obtained by the production method of the present invention is preferably less than 1.05. Furthermore, the number average molecular weight (Mn) is preferably 200 to 1,500, and the weight average molecular weight (Mw) is preferably 200 to 1,500.

[0040] Unless otherwise specified in the specification, the average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are based on so-called PEO-reduced molecular weight, which is determined by gel permeation chromatography (GPC) using polyethylene oxide (PEO) as a reference.

[0041] Gel permeation chromatography measurements can be performed under the following conditions, for example. Equipment: HLC-8320GPC EcoSEC (manufactured by Tosoh Corporation) Column: One each of TSKgel guardcolumn SuperAW, TSKgel SuperAW4000, TSKgel SuperAW3000, and TSKgel SuperAW2500 (all manufactured by Tosoh Corporation) connected together. Sample solution: 0.01 M lithium bromide dimethylformamide solution Solution injection volume: 20μl Sample concentration: 5 mg / 4 ml (0.125%) Flow rate: 0.6ml / min Measurement temperature: 40℃ Detection device: Refractive index detector Reference substance: Standard polyethylene glycol

[0042] The aliphatic alcohol ethylene oxide adduct obtained by the production method of the present invention has a narrow molecular weight distribution and can be preferably used as a detergent, cosmetic, metalworking fluid, spreading agent for pesticides, and surfactant for pesticides. Furthermore, because the addition of ethylene oxide is uniform, it can be particularly suitable for use as a surfactant with excellent performance in areas such as emulsification stability, cleaning ability, foaming ability, and defoaming ability. [Examples]

[0043] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, parts refer to parts by weight.

[0044] <Example 1> In a stainless steel autoclave equipped with stirring, temperature control functions, and a tube for introducing ethylene oxide from the bottom of the device, 158 parts (1 mole) of aliphatic monoalcohol (a-1) (Decanol, manufactured by KH Neochem Co., Ltd.; 10 carbon atoms) and 0.023 parts of DMC catalyst (DMC CATALYST; manufactured by Huaian Bud Polyurethane Science & Technology Co. Ltd.; composition: Zn3[Co(CN)6]2·2.48DME·4.65H2O·0.94ZnCl2) were added. After purging the mixture with nitrogen, dehydration was carried out under reduced pressure at 120°C for 1 hour. Next, 308 parts (7 moles) of ethylene oxide were introduced at 130°C over 7.4 hours to obtain an ethylene oxide adduct of an aliphatic alcohol (A-1). The calculated value of the formula <[(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Introduction time of ethylene oxide (hours)]> was 0.9 (7 / 1 / 7.4).

[0045] <Example 2> In a stainless steel autoclave equipped with stirring, temperature control functions, and a tube for introducing ethylene oxide from the bottom of the device, 186 parts (1 mole) of aliphatic monoalcohol (a-2) ("Calcol 2098" manufactured by Kao Corporation; 12 carbon atoms) and 0.029 parts of the same DMC catalyst as in Example 1 were added. After purging the mixture system with nitrogen, dehydration was carried out under reduced pressure at 120°C for 1 hour. Next, 396 parts (9 moles) of ethylene oxide were introduced at 130°C over 9.5 hours to obtain an ethylene oxide adduct of an aliphatic alcohol (A-2). The calculated value of the formula <[(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Introduction time of ethylene oxide (hours)]> was 0.9 (9 / 1 / 9.5).

[0046] <Comparative Example 1> An ethylene oxide adduct of an aliphatic alcohol (A'-1) was obtained in the same manner as in the addition reaction step of Example 1, except that the introduction time of ethylene oxide in the addition reaction step of Example 1 was changed to 6.0 hours. The calculated value of the formula <[(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Introduction time of ethylene oxide (hours)]> was 1.2 (7 / 1 / 6.0).

[0047] <Comparative Example 2> Except for changing the catalyst species in the addition reaction step of Example 1 to 0.233 parts of potassium hydroxide (KOH) and changing the introduction time of ethylene oxide to 7.7 hours, the addition reaction step of an aliphatic alcohol ethylene oxide adduct (A'-2) was obtained in the same manner as in Example 1. The calculated value of the formula <[(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Introduction time of ethylene oxide (hours)]> was 0.9 (7 / 1 / 7.7).

[0048] <Comparative Example 3> An ethylene oxide adduct of an aliphatic alcohol (A'-3) was obtained in the same manner as in the addition reaction step of Example 2, except that the introduction time of ethylene oxide in the addition reaction step of Example 2 was changed to 7.5 hours. The calculated value of the formula <[(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Introduction time of ethylene oxide (hours)]> was 1.2 (9 / 1 / 7.5).

[0049] For each aliphatic monoalcohol ethylene oxide adduct (A) obtained above, molecular weight was measured using GPC and the Mw / Mn ratio was calculated. The results are shown in Table 1.

[0050] [Table 1]

[0051] Under manufacturing conditions where the total number of moles of ethylene oxide used in the reaction step, the total number of moles of aliphatic monoalcohols, and the introduction time of ethylene oxide in the reaction step satisfy the relationship <1.0 ≥ [(total number of moles of ethylene oxide) / (total number of moles of aliphatic monoalcohols)] / [introduction time of ethylene oxide (hours)]>, the ethylene oxide adducts of aliphatic alcohols (A-1) to (A-2) obtained showed a narrower molecular weight distribution compared to the ethylene oxide adducts of the comparative example.

[0052] <Example of evaluation: Evaluation of penetration power> For the aliphatic monoalcohol ethylene oxide adducts obtained in Examples 1-2 and Comparative Examples 1 and 3 ((A-1), (A-2), (A'-1), and (A'-3), respectively), 0.01% by mass aqueous solutions were prepared and used as test solutions. A 15mm x 15mm cotton canvas disc was gently floated in a beaker containing 200mL of the test solution, which had been heated to 20°C. The time it took for the cotton canvas disc to sink below the water surface and begin to settle (hereinafter referred to as "settling start time") (seconds) was measured using a stopwatch. The measurement was repeated 10 times for each sample, and the average value of the sedimentation start time was calculated. Furthermore, a shorter sedimentation start time was considered to indicate higher permeability. As a result, the sedimentation start time for the 0.01 mass% aqueous solution of (A-1) was 11 seconds, which was, on average, 2 seconds shorter than the sedimentation start time of 13 seconds for the 0.01 mass% aqueous solution of (A'-1), which used the same aliphatic monoalcohol and catalyst species. Furthermore, the sedimentation start time for the 0.01 mass% aqueous solution of (A-2) was 28 seconds, which was, on average, 5 seconds shorter than the sedimentation start time of 33 seconds for the 0.01 mass% aqueous solution of (A'-3), which used the same aliphatic monoalcohol and catalyst species. Based on the above, it was confirmed that the aliphatic monoalcohol ethylene oxide adduct with a narrow molecular weight distribution obtained by the present manufacturing method has excellent penetrating power. [Industrial applicability]

[0053] The aliphatic alcohol ethylene oxide adduct of the present invention has a narrow molecular weight distribution and can therefore be suitably used as various surfactants, solvents, and chemical intermediates. Furthermore, the aliphatic monoalcohol ethylene oxide adduct obtained by the production method of the present invention can be suitably used in applications such as detergents, cosmetics, metalworking fluids, spreading agents for agricultural chemicals, and agricultural chemicals. Moreover, because the narrow molecular weight distribution improves penetration power, it can be suitably used in applications where the imparting or improvement of penetration is required.

Claims

[Claim 1] A method for producing an aliphatic alcohol ethylene oxide adduct, comprising a reaction step of introducing ethylene oxide into a reaction vessel containing an aliphatic monoalcohol having 8 to 24 carbon atoms in the presence of a bimetallic cyanide complex, A method for producing an aliphatic alcohol ethylene oxide adduct, wherein the ratio of moles of ethylene oxide to moles of aliphatic monoalcohol is 2 / 1 to 20 / 1, and the total number of moles of ethylene oxide used in the reaction step, the total number of moles of aliphatic monoalcohol, and the introduction time of ethylene oxide in the reaction step satisfy the following relationship. 1.0 ≥ [(Total number of moles of ethylene oxide) / (Total number of moles of aliphatic monoalcohols)] / [Time of introduction of ethylene oxide (hours)]

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