JP2010265187A - Method for producing fatty acid polyoxyalkylene alkyl ether reduced in by-products - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fatty acid polyoxyalkylene alkyl ether in which the addition molar distribution of an alkylene oxide is narrow, and the yield of a polyalkylene glycol as a by-product can be reduced. <P>SOLUTION: The method for producing the fatty acid polyoxyalkylene alkyl ether includes a process for addition-reacting a fatty acid ester with an alkylene oxide in the presence of a calcined alumina-magnesia co-oxide catalyst in the coexistence of a base substance selected from alkali metal carbonates, silicates and carboxylates and organic amines having a molecular weight of <1,000 and quaternary salts thereof. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a calcined alumina-magnesia composite oxide catalyst coexisting with a basic substance selected from alkali metal carbonates, silicates and carboxylates, organic amines having a molecular weight of less than 1000 and quaternary salts thereof. The present invention relates to a method for producing a fatty acid polyoxyalkylene alkyl ether by adding an alkylene oxide to a fatty acid ester in the presence.

Alkylene oxide adducts of fatty acid esters are known as ester-type nonionic surfactants, and are used as emulsifiers, dispersants and the like in various industrial fields. A calcined alumina / magnesia composite oxide catalyst is known as a solid catalyst for performing a reaction of directly adding an alkylene oxide to a fatty acid ester. When an alkylene oxide is added to a fatty acid ester using the above catalyst, the distribution of the number of added alkylene oxides in the product alkylene oxide is widened, and many unreacted fatty acid esters remain. As a catalyst that narrows the distribution of the added mole number and suppresses the remaining unreacted component, a catalyst obtained by treating the catalyst with a metal hydroxide or a metal alkoxide is known (Patent Document 1).
When such a reaction of directly adding alkylene oxide to a fatty acid ester using a calcined alumina / magnesia composite oxide catalyst treated with a metal hydroxide or a metal alkoxide, an alkylene oxide adduct having a narrow addition mole number distribution is performed. However, there was a problem that a large amount of polyalkylene glycol having a molecular weight of tens of thousands was produced. In order to solve this problem, a catalyst for alkoxylation, which is spherical metal oxide particles containing at least one metal selected from Group 6A, Group 7A and Group 8, magnesium, and aluminum, has been studied. (Patent Document 2).
However, when an alkylene oxide is added to a fatty acid ester using an existing catalyst, the generation of polyalkylene glycol as a by-product is sufficiently suppressed, and the fatty acid polyoxyalkylene alkyl ether having a narrow range of addition molar distribution of alkylene oxide. In particular, when propylene oxide is subjected to an addition reaction, the by-produced polypropylene glycol is problematic because it cannot be removed by filtration.

Japanese Patent Laid-Open No. 8-169861 JP 2001-314765 A

  An object of the present invention is to provide a method for producing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of alkylene oxide capable of suppressing the amount of polyalkylene glycol as a by-product, and a catalyst used in this method. To do.

As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by using a magnesium / aluminum catalyst coexisting with a specific basic substance.
That is, the present invention
In the presence of a calcined alumina-magnesia composite oxide catalyst coexisting with a basic substance selected from alkali metal carbonates, silicates and carboxylates and organic amines having a molecular weight of less than 1000 and quaternary salts thereof, A method for producing a fatty acid polyoxyalkylene alkyl ether represented by the following formula (1), which comprises a step of subjecting a fatty acid ester to an alkylene oxide addition reaction;
_{^{R 1 COO (AO) n R}} 2 ··· (1)
(In the formula, R ¹ is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 5 to 21 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is larger than 1. The case may be the same or different, and R ² is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 8 carbon atoms, and n is 1 ≦ n ≦ 20).
Further, the present invention treats a calcined alumina / magnesia composite oxide catalyst with a basic substance selected from alkali metal carbonates, silicates and carboxylates, organic amines having a molecular weight of less than 1000 and quaternary salts thereof. And a catalyst for producing a fatty acid polyoxyalkylene alkyl ether.

  According to the present invention, it is possible to produce a fatty acid polyoxyalkylene alkyl ether having a narrow addition mole number distribution of alkylene oxide while suppressing the amount of polyalkylene glycol, which is a by-product, as compared with conventional methods. In particular, the present invention is advantageous in that the amount of polypropylene glycol generated when propylene oxide is used can be suppressed.

(A) A calcined alumina / magnesia composite oxide catalyst The calcined alumina / magnesia composite oxide catalyst used in the present invention is a catalyst represented by the following formula (2) or a hydrotalcite represented by the following formula (3). A catalyst obtained by calcination is preferred.
nMgO.Al ₂ O ₃ .mH ₂ O (2)
(N is 2 to 18, preferably 2 to 8, particularly preferably 2.5, and m is 0 to 20, preferably 0 to 12)
[Mg ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^{X +} [A ^n-1 _{x / n} · mH ₂ O] ^x- (3)
(X is 0.1 ≦ x ≦ 0.5, and 0.25 ≦ x ≦ 0.45 is particularly preferable, and A ^n-1 is CO ₃ ²⁻ , SO ₄ ⁻² , OH ⁻ , NO ₃ ^−. , Fe (CN) ₆ ^3- or CH ₃ COO ^- represents an anion selected from).
The firing temperature is preferably 400 to 950 ° C, more preferably 400 to 900 ° C. The firing time is preferably 0.5 to 12 hours, and more preferably 1 to 5 hours.

Examples of the calcined alumina / magnesia composite oxide catalyst include calcined hydrotalcite described in JP-A-2-71841, calcined aluminum hydroxide / magnesium described in JP-A-8-268919, and the like. An Al—Mg based complex oxide catalyst or the like can be used.
Among these catalysts, a catalyst having an Al / Mg molar ratio of 0.1 / 0.9 to 0.5 / 0.5, and further 0.25 / 0.75 to 0.45 / 0.55 is used. It is preferable to do. By increasing the Al / Mg molar ratio from 0.1 / 0.9, the reactivity can be increased, and by reducing the Al / Mg molar ratio from 0.5 / 0.5, the amount of by-products generated can be suppressed.

(B) Basic substance Any basic substance selected from alkali metal carbonates, silicates and carboxylates, organic amines having a molecular weight of less than 1000, and quaternary salts thereof can be used without particular limitation. Examples of the alkali metal carbonate include potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate and the like. Examples of the alkali metal silicate include potassium silicate, sodium metasilicate, and sodium orthosilicate. Examples of the alkali metal carboxylate include sodium acetate and sodium stearate. Examples of the organic amine having a molecular weight of less than 1,000 include primary amines such as 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-lauryloxypropylamine, octadecylamine, diisobutylamine, and di-2. -Secondary amines such as ethylhexylamine, dibenzylamine, di-n-octylamine, tertiary such as trimethylamine, triethylamine, tri-n-octylamine, tributylamine, triethanolamine, dimethyloctylamine, dimethyllaurylamine Amines, cyclic amines such as indoline, pyrrolidone, pyrrole, pyrazole, pyridine, quinoline, 4-benzylpyridine, quinuclidine, imidazoline, polyoxyethylene palm alkylamine, polyoxyethylene olei Polyoxyalkylene alkylene amines such as amine, N, N-bis (3-aminopropyl) dodecylamine, polyamines having a plurality of amino groups such as N-cocoalkyl 1,3-diaminopropane, phosphazene type containing a phosphorus atom, Examples include proazaphosphatran type amines. Examples of the quaternary salt of the amine include tetramethylammonium chloride and tetraethylammonium hydroxide. Among these organic amines, it is preferable to select primary to tertiary amines and cyclic amines.

Among these basic substances, it is more preferable to select a basic substance having an acid dissociation constant (pKa) of the conjugate acid generated in water at 25 ° C. in the range of 9 to 12. Thus, substances having a pKa value in the range of 9 to 12 include, for example, tri-n-octylamine (pKa = 10.38), quinuclidine (pKa = 10.65), potassium carbonate (pKa = 10.2). ), Sodium carbonate (pKa = 10.2). The method for measuring the acid dissociation constant (pKa) is not particularly limited, but as a method for experimentally examining, a usual titration method can be mentioned. In addition, it is possible to examine the pKa known from the literature such as the chemical handbook (Chemical Society of Japan <Maruzen Co., Ltd.>), and it is also possible to calculate from the compound structure by calculation software such as ACD / pKa DB. It is.
In addition, when performing the water removal step described later, it is preferable to use a basic substance having a boiling point higher than 150 ° C among these basic substances. Examples of such basic substances include potassium carbonate and sodium carbonate. A carbonate having a bulky alkyl group (for example, an alkyl group having 6 to 18 carbon atoms) such as 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-lauryloxypropylamine, Octadecylamine, di-2-ethylhexylamine, dibenzylamine, indoline, pyrrolidone, di-n-octylamine, pyrazole, tri-n-octylamine, tributylamine, dimethyloctylamine, dimethyllaurylamine, quinoline, 4-benzyl Pyridine, triethanolamine, quinuclidine Polyoxyethylene coconut alkyl amine, polyoxyethylene oleyl amine, N, N- bis (3-aminopropyl) dodecylamine, be selected such N- coconut alkyl 1,3-diaminopropane preferred.

(C) Fatty acid ester The fatty acid ester used as a starting material is a compound represented by the following formula (4).
R ₁ COOR ₂ (4)
In the formula, R ¹ is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 5 to 21 carbon atoms, preferably 7 to 19 carbon atoms, more preferably 11 to 17 carbon atoms. R ² is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of these fatty acid esters include methyl heptanoate, ethyl heptanoate, isopropyl heptanoate, isobutyl heptanoate, 2-ethylhexyl heptanoate, methyl caprate, ethyl caprate, isopropyl caprate, isobutyl caprate, 2-caprate Ethylhexyl, methyl laurate, ethyl laurate, isopropyl laurate, isobutyl laurate, -2-ethylhexyl laurate, methyl myristate, ethyl myristate, isopropyl myristate, isobutyl myristate, 2-ethylhexyl myristate, palmitic acid Methyl, ethyl palmitate, isopropyl palmitate, isobutyl palmitate, 2-ethylhexyl palmitate, methyl stearate, ethyl stearate, Isopropyl allate, isobutyl stearate, 2-ethylhexyl stearate, methyl oleate, ethyl oleate, isopropyl oleate, isobutyl oleate, 2-ethylhexyl oleate, methyl linoleate, ethyl linoleate, isopropyl linoleate, Isobutyl linoleate, 2-ethylhexyl linoleate, methyl linolenate, ethyl linolenate, isopropyl linolenate, isobutyl linolenate, 2-ethylhexyl linolenate can be used. Of these, methyl laurate, ethyl laurate, isopropyl laurate, isobutyl laurate, 2-ethylhexyl laurate, methyl myristate, ethyl myristate, isopropyl myristate, isobutyl myristate, 2-ethylhexyl myristate , Methyl palmitate, ethyl palmitate, isopropyl palmitate, isobutyl palmitate, 2-ethylhexyl palmitate, methyl stearate, ethyl stearate, isopropyl stearate, isobutyl stearate, 2-ethylhexyl stearate, methyl oleate , Ethyl oleate, isopropyl oleate, isobutyl oleate, 2-ethylhexyl oleate, methyl linoleate, ethyl linoleate, isolinoleate Propyl, isobutyl linoleate, it is used linoleic acid-2-ethylhexyl, preferable because it is easy to handle during ease and manufacturing availability. Furthermore, among these, methyl laurate, isopropyl laurate, isobutyl laurate, 2-ethylhexyl laurate, methyl myristate, isopropyl myristate, isobutyl myristate, 2-ethylhexyl myristate, methyl palmitate, palmitate Isopropyl acid, isobutyl palmitate, 2-ethylhexyl palmitate, methyl stearate, isopropyl stearate, isobutyl stearate, 2-ethylhexyl stearate are compounds with few double bonds in the molecule and excellent oxidation stability. Since it is obtained, it is more preferable. Examples of such commercially available fatty acid esters include pastel M-12, pastel M-14, pastel M-16, pastel M-180, pastel M-181, pastel M-182, pastel 2H-08, pastel 2H- 16 (Lion Corporation products) can be used. In the present invention, the above fatty acid esters can be used alone or in combination of two or more.

(D) Alkylene oxide As the alkylene oxide to be subjected to addition polymerization, those having 2 to 4 carbon atoms (2 to 4 carbon atoms in A) are preferable, and ethylene oxide and propylene oxide having 2 to 3 carbon atoms are particularly preferable. The alkylene oxides can be used alone or as a mixture of two or more. The method of the present invention is advantageous in that the amount of polypropylene glycol, which is a byproduct, can be suppressed, particularly when propylene oxide is used.

(E) Method for Producing Fatty Acid Polyoxyalkylene Alkyl Ether The production method of the present invention is selected from a catalyst and an alkali metal carbonate, silicate and carboxylate, an organic amine having a molecular weight of less than 1000, and a quaternary salt thereof. The addition of alkylene oxide is carried out in the presence of a basic substance. As described above, the method of coexisting the catalyst and the basic substance can employ a method of adding the catalyst and the basic substance into the reaction vessel. However, as described below, the catalyst is made of an alkali metal in advance. It is also possible to treat with a basic substance selected from carbonates, silicates and carboxylates, organic amines with a molecular weight of less than 1000 and their quaternary salts, and use such treated catalysts in addition reactions. it can.
A method for treating such a calcined alumina / magnesia composite oxide catalyst is not particularly limited, but the calcined alumina / magnesia composite oxide catalyst is used as an aqueous solution of the basic substance (the solution concentration is the amount of the basic substance relative to the catalyst. The method of spraying (for example, using a solution of 10 to 60% by mass) and drying (100 ° C. to 120 ° C. for 30 to 180 minutes) can be suitably used. The aqueous solution may contain an alcohol such as ethanol, methanol and propanol, or a ketone solvent such as acetone which does not contain an OH group.

The reaction of the present invention can be easily carried out under ordinary operating procedures and reaction conditions. The reaction temperature is 80 to 230 ° C, preferably 120 to 180 ° C. The reaction pressure is 0 to 2 MPa, preferably 0.2 to 0.8 MPa, although it depends on the reaction temperature. Although the usage-amount of a catalyst changes also with the molar ratio of the alkylene oxide and fatty acid ester with which it uses for reaction, 0.1-10 mass% of the amount of fatty acid esters is preferable normally.
In the reaction of the present invention, for example, a fatty acid ester and a catalyst treated as described above are charged in an autoclave, degassed and dehydrated, and then an alkylene oxide is added under a predetermined temperature and pressure in a nitrogen atmosphere. The reaction can then be carried out by cooling the reaction and filtering off the catalyst.
Further, as another method, fatty acid ester, calcined alumina / magnesia composite oxide catalyst and basic substance are added and mixed in the autoclave, degassing and dehydrating treatment are performed as described above, and then a predetermined reaction temperature, It can also be carried out by addition polymerization of alkylene oxide under pressure and atmosphere, further cooling the reaction solution and separating the catalyst. In this method, the order of addition of the raw material fatty acid ester, the calcined alumina / magnesia composite oxide catalyst and the basic substance is not particularly limited. At this time, it is preferable to add the basic substance as a solution in which the basic substance is dispersed in a lower alcohol or various solvents because the catalytic surface active sites can be more uniformly and selectively modified.
In the method of the present invention, the amount of the basic substance with respect to 100 parts by mass of the calcined alumina / magnesia composite oxide catalyst is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and further more preferably 5 to 12 parts by mass. preferable. By setting the amount of the basic substance to 1 part by mass or more, it can sufficiently act on Al which is an active site, and the production of polyalkylene glycol can be suppressed. In addition, by making the amount of the basic substance 20 parts by mass or less, it is possible to prevent excessive modification to Al which is an active site and to prevent excessive addition of alkylene oxide.

By adding the water content of the reaction system to 60 ppm or less before adding the alkylene oxide, the generation of by-products (polyalkylene glycol) and the turbidity of the liquid appearance due to the insoluble polyalkylene glycol are more efficiently performed. Can be suppressed. As a result of studies by the present inventors, it has been found that the amount of polyalkylene glycol produced can be suppressed to some extent only by adjusting the water content. Therefore, adding a step of adjusting the amount of water to the production method of the present invention is also effective in suppressing the amount of polyalkylene glycol produced.
By controlling the amount of water in the reaction system before addition of alkylene oxide to 200 ppm or less, and even more preferably 60 ppm or less, the amount of polyalkylene glycol, which is a byproduct, is suppressed, and the liquid appearance is kept transparent. it can.
By setting the amount of water before addition of alkylene oxide to 60 ppm or less, OH groups, which are starting materials for side reactions, can be reduced, and by-products can be more efficiently reduced. The dehydration method for reducing the water content before addition of alkylene oxide to 60 ppm or less is not particularly limited, but the following is preferable.
(A) Dehydration method at a high vacuum level with a vacuum level of 0.4 KPa or less. The temperature is preferably as high as possible, but is carried out, for example, at 60 ° C. or higher until the target moisture value is reached.
(B) A dehydration method at a high temperature of 160 ° C. or higher. The degree of decompression is preferably as low as possible, but is performed until the target moisture value is reached at 1.3 KPa or less, for example.
(C) A method in which ethanol is added to form an azeotrope with water and then dehydrated by distillation. The temperature is preferably near the boiling point of the azeotropic mixture, and the pressure during distillation is preferably normal pressure. For example, the temperature is 50 ° C. to 120 ° C. until the target moisture value is reached.
(D) A dehydration method by bubbling using N ₂ . For example, the temperature is 40 ° C. to 150 ° C. and the pressure is +13.3 KPa or less until the target moisture value is reached.
(E) a N ₂ was introduced to 0.1 MPa, followed 1.0KPa by operation of vacuum to below, the dehydration method of removing by entrainment of N ₂ and water. For example, the temperature is 60 ° C. to 150 ° C., the N ₂ introduction pressure is 0.2 MPa or less, and the degree of vacuum is 1.0 KPa or less until the target moisture value is reached.
Among these methods, the use of the methods (a), (d), and (e) can be dehydrated to the target moisture amount relatively inexpensively without affecting the quality. preferable.

(F) Obtained fatty acid polyoxyalkylene alkyl ether By the method of this invention, the compound represented by following formula (1) can be obtained.

R ¹ COO (AO) _n R ² (1)

In the formula, R ¹ is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 5 to 21 carbon atoms, preferably 7 to 19 carbon atoms, more preferably 11 to 17 carbon atoms. A is an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, more preferably 3 carbon atoms, and when n is larger than 1, they may be the same or different. R ² is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
n is 1 ≦ n ≦ 20, preferably 3 ≦ n ≦ 12, more preferably 5 ≦ n ≦ 9. It is preferable that n is 1 or more because the remaining amount of unreacted fatty acid ester is small and the problem of odor is less likely to occur. When n is 20 or less, an excessive increase in viscosity due to an excessively high molecular weight of the product can be suppressed, and in the purification process for removing the solid catalyst, the filtration time can be shortened and the number of filtrations can be reduced. Is preferable because the manufacturing cost can be suppressed.
R ¹ is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 11 to 17 carbon atoms, A is an alkylene group having 2 to 3 carbon atoms, and n is greater than 1, or the same or The raw material is that R ² is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 8 carbon atoms, and n is 1 ≦ n ≦ 20. Since it is easy to obtain fatty acid esters and alkylene oxides, it is more preferable. R ¹ is a linear or branched monovalent saturated or unsaturated hydrocarbon group having 11 to 17 carbon atoms, A is an alkylene group having 2 to 3 carbon atoms which may be the same or different, and R ^More preferably, ² is a linear or branched monovalent saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms, and n is 3 ≦ n ≦ 12.

  By the method of the present invention, a fatty acid polyoxyalkylene alkyl ether having a narrow distribution of added mole number of alkylene oxide can be produced. Here, when the average number of added moles is the same, the remaining amount of unreacted fatty acid ester decreases as the added mole number distribution becomes narrower and sharper.

  Moreover, the generation amount of polyalkylene glycol as a by-product can be suppressed by using the method of the present invention. In the present invention, the polyalkylene glycol as a by-product means a polyalkylene glycol having a number average molecular weight of 10,000 or more. The number average molecular weight is a value measured by gel permeation chromatography based on polyethylene glycol. By using the method of the present invention, the generated amount of polyalkylene glycol as a by-product is 0.1% by mass or less, preferably 0. It can be suppressed to 05 mass% or less, more preferably 0.01 mass% or less.

Example 1
_{2.5MgO · Al 2 O 3 · mH} 2 O of alumina magnesia complex oxide (Kyowa Chemical Industry Co., Kyoward 300) under a nitrogen stream, then calcined 3 hours at 750 ° C., calcined alumina-magnesia (Al / Mg molar Ratio = 0.44 / 0.56) A composite oxide catalyst was obtained. In a 4 L autoclave, 617 g of methyl laurate (fatty acid methyl ester derived from palm oil derived from a carbon number 12 fraction, trade name: Pastel M12, manufactured by Lion Corporation), 14.4 g of the catalyst as a basic substance, K ₂ 0.80 g of CO ₃ powder (Pure Chemicals reagent, special grade) was charged, and nitrogen substitution was performed. Subsequently, in order to remove the water | moisture content contained in a raw material, it heated up to 100 degreeC and performed 1-h dehydration process at 0.4 kPa. After the dehydration treatment, the water content before the propylene oxide (PO) addition reaction was 48 ppm. Thereafter, the temperature was raised to 180 ° C., the inside of the reaction vessel was returned to normal pressure with nitrogen, and 1169 g of PO (equivalent to 7 mol per 1 mol of methyl laurate) was gradually dropped into the vessel. Immediately after completion of the dropping, the pressure of 0.34 MPa decreased with the progress of the reaction, and PO addition reaction was continued until the pressure became constant at 0.29 MPa after 2 hours. As a result of analyzing the obtained reaction liquid before filtration by high performance liquid chromatography, polypropylene glycol (PPG) was trace. Subsequently, 20.25 g (1.5% by mass with respect to the reaction solution) of Hyflo Supercell (manufactured by Celite: diatomaceous earth) was added to 1350 g of the reaction solution, and uniformly dispersed, and then pressure filtration was performed at 80 ° C. . As a result of analyzing the obtained reaction liquid after filtration by high performance liquid chromatography, PPG was trace and the amount of cloudy precipitate was 2 ml. Moreover, as a result of analyzing the obtained purified product by gas chromatography, the residual amount of unreacted methyl laurate was 2.1% by mass.

(Example 2)
The same procedure as in Example 1 was performed except that 1.60 g of K ₂ CO ₃ powder was used as the basic substance. The water content before PO addition was 54 ppm. The PPG before filtration was trace, the PPG after filtration was trace, and the amount of white turbid precipitate was 3 ml. Moreover, the unreacted methyl laurate residual amount was 0.8 mass%.

(Example 3)
The same procedure as in Example 1 was performed except that 0.61 g of Na ₂ CO ₃ powder (Pure Chemicals reagent, special grade) was used as the basic substance. The water content before PO addition was 44 ppm. The PPG before filtration was trace, the PPG after filtration was trace, and the amount of white turbid precipitate was 2 ml. Moreover, the unreacted methyl laurate residual amount was 2.5 mass%.

Example 4
The same procedure as in Example 1 was performed except that 2.04 g of tri-n-octylamine (Koei Chemical Industry Reagent) was used as the basic substance. The amount of water before addition of PO was 53 ppm. The PPG before filtration was trace, the PPG after filtration was trace, and the amount of white turbid precipitate was 7 ml. Moreover, the residual amount of unreacted methyl laurate was 3.8% by mass.

(Example 5)
The same procedure as in Example 1 was performed except that 0.64 g of quinuclidine (a reagent manufactured by Junsei Kagaku, special grade) was used as a basic substance. The water content before PO addition was 51 ppm. The PPG before filtration was trace, the PPG after filtration was trace, and the amount of white turbid precipitate was 6 ml. Moreover, the unreacted methyl laurate residual amount was 2.2 mass%.

(Example 6)
As raw material fatty acid methyl esters, 755 g of methyl oleate (product name: Pastel M-182, iodine number: 91) manufactured by Lion Corporation, 1.60 g of K ₂ CO ₃ powder, 1031 g of PO (based on 1 mol of methyl oleate) The reaction was performed in the same manner as in Example 1 except that it was used. The water content before PO addition was 51 ppm. The PPG before filtration was trace, the PPG after filtration was trace, and the amount of white turbid precipitate was 1 ml. Moreover, the unreacted methyl oleate residual amount was 1.4 mass%.

(Example 7)
The same procedure as in Example 1 was performed except that 724 g of methyl laurate and 1064 g of EO (equivalent to 7 mol per 1 mol of methyl laurate) were used as the raw material fatty acid methyl ester. The amount of water before EO addition was 50 ppm. The PEG (polyethylene glycol) before filtration was 0.27% by mass, the PEG after filtration was trace, and the amount of white turbid precipitate was 8 ml. Moreover, the unreacted methyl laurate residual amount was 1.0 mass%.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that 0.82 g of a 40% by mass aqueous solution of KOH (Pure Chemicals reagent, special grade) was used in place of the K ₂ CO ₃ powder. The water content before PO addition was 50 ppm. The PPG before filtration was 0.60% by mass, the PPG after filtration was 0.61% by mass, and the amount of white turbid precipitate was 19 ml. Moreover, the unreacted methyl laurate residual amount was 2.0 mass%.

(Comparative Example 2)
K ₂ CO ₃ instead of powder, except that 50 wt% CsOH aqueous solution (manufactured by Kanto Kagaku) was used 1.75 g, it was performed in the same manner as in Example 1. The water content before PO addition was 52 ppm. The PPG before filtration was 0.76% by mass, the PPG after filtration was 0.63% by mass, and the amount of white turbid precipitate was 40 ml. Moreover, the unreacted methyl laurate residual amount was 0.4 mass%.

(Comparative Example 3)
The same procedure as in Example 1 was carried out except that 1.11 g of a 28% by mass NaOMe methanol solution (manufactured by Junsei Kagaku) was used in place of the K ₂ CO ₃ powder. The water content before PO addition was 54 ppm. The PPG before filtration was 1.45% by mass, the PPG after filtration was 0.78% by mass, and the amount of white turbid precipitate was 15 ml. Moreover, the residual amount of unreacted methyl laurate was 5.2% by mass.

Each Example and Comparative Example manufactured as described above were evaluated by the following evaluation methods.
(1) Evaluation method (i) Appearance The filtered reaction liquid obtained in each of the examples and comparative examples is heated at 80 ° C. for 30 minutes and dissolved uniformly. Thereafter, 100 ml was collected in a 100 mL colorimetric tube (inner diameter 25 mm × length 200 mm), cooled to 20 ° C., and the amount of cloudy precipitate after 72 hours was read with the value of the colorimetric tube scale.
Point Amount of cloudy sediment (ml)
5 points 0
4 points 2 to 10
3 points 10-20
2 points 20-50
1 point 50 or more

(2) Analytical method (i) Quantification of PPG / PEG Quantification of polymer PPG (polypropylene glycol) / PEG (polyethylene glycol) by-produced by the reaction was carried out as follows. Since these high molecular weight impurities cause poor appearance and reduce the yield of the target product, it is desirable that these impurities be close to zero. In addition, 100 ppm or less was made into trace.
(A) When the by-product is PPG As a standard substance, 0.25 g of PPG 10000 (Preminol, manufactured by Asahi Glass Co., Ltd., molecular weight 10,000) is diluted with 25 ml of high-performance liquid chromatography THF (manufactured by Junsei Kagaku), and a 1% PPG solution did. Further, a calibration curve was prepared using a PPG solution diluted with THF and having different concentrations.
0.25 g of sample was made up to 25 ml with THF, and 2000 μl was injected. PPG contained in the sample was quantified from the obtained peak height and calibration curve.

Equipment conditions High performance liquid chromatogram: PLC-561 (manufactured by GL Sciences)
Detector: RI-704 (manufactured by GL Science), column: Diol (20φ × 250 mm), temperature: 40 ° C., solvent: THF (manufactured by Junsei Chemical Co., Ltd. for high performance liquid chromatography), flow rate: 5 ml / min

(B) When the by-product is PEG 0.15 g of PEG (Polyethylene oxide, manufactured by Tosoh Corp., molecular weight of about 45,000) as a standard substance is diluted with 10 ml of acetonitrile / H ₂ O solvent for analysis, and the concentration is 1.5%. A PEG solution was obtained. Further, a calibration curve was prepared using a PEG solution that had been diluted with an analytical solvent and changed in concentration.
Dilute 0.2 g of sample with 10 ml of analytical solvent and inject 200 μl. Quantification of PEG contained in the sample was performed from the obtained peak height and calibration curve.

Apparatus conditions High performance liquid chromatogram: Detector: RID-10A (manufactured by Shimadzu Corporation), column: GF-310HQ (manufactured by Showa Denko), temperature: 30 ° C., solvent: acetonitrile / H ₂ O = 45/55, acetonitrile (Kanto) Chemical high performance liquid chromatography), distilled water (manufactured by Wako Pure Chemical Industries), flow rate: 0.6 ml / min

(Ii) Quantification of unreacted fatty acid methyl ester After 0.5 g of the methyl ester sample used in each example and comparative example was uniformly dissolved in 5 ml of acetone, 1 μl was injected using a microsyringe and analyzed. Unreacted fatty acid methyl ester was quantified using each peak area of the obtained chromatogram.

Apparatus conditions Gas chromatogram: HP-5890 (manufactured by Hewlett Packard), detector: FID (manufactured by Hewlett Packard), column: ULTRA-2 (length 25 m × ID 0.2 mm × film thickness 0.11 μm), solvent: acetone (genuine) Chemical, special grade), temperature: initial 80 ° C. (2 min hold) → temperature rise (5 ° C./min)→100° C. → temperature rise (25 ° C./min)→320° C. (20 min hold), split vent flow rate: 50 ml / min, purge vent flow rate: 3.5 ml / min, split ratio: 1/50, INJECTION: 300 ° C., DETECTOR: 320 ° C.

(Iii) Measurement of moisture content before addition of alkylene oxide The apparatus was turned on and stirred for about 1 hour to stabilize the solution. Thereafter, about 2 g of the sample was injected and measured using a 2 ml poly dropper. The measurement was performed by Karl Fischer coulometric titration.

Equipment conditions: Trace moisture measuring device: AQ-7 (manufactured by Hiranuma Sangyo), generated liquid: Hydranal Aqualite RO, measurement mode: Medium

Table 1 below shows the evaluation results of the examples and the comparative examples according to the above evaluation method.

Claims (7)

In the presence of a calcined alumina-magnesia composite oxide catalyst coexisting with a basic substance selected from alkali metal carbonates, silicates and carboxylates and organic amines having a molecular weight of less than 1000 and quaternary salts thereof, A method for producing a fatty acid polyoxyalkylene alkyl ether represented by the following formula (1), which comprises a step of subjecting a fatty acid ester to an addition reaction of an alkylene oxide;
R ¹ COO (AO) _n R ² (1)
(In the formula, R ¹ is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 5 to 21 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is larger than 1. The case may be the same or different, and R ² is a monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 8 carbon atoms, and n is 1 ≦ n ≦ 20).   The production method according to claim 1, wherein the basic substance is a basic substance having an acid dissociation constant (pKa) of a conjugate acid generated in water at 25 ° C in a range of 9 to 12.   The production method according to claim 1 or 2, wherein the organic amine is a primary to tertiary amine or a cyclic amine.   The production method according to any one of claims 1 to 3, wherein 1 to 20 parts by mass of the basic substance coexist with 100 parts by mass of the calcined alumina / magnesia composite oxide catalyst.   The manufacturing method according to any one of claims 1 to 4, wherein the calcined alumina / magnesia composite oxide catalyst has an Al / Mg molar ratio of 0.1 / 0.9 to 0.5 / 0.5. The calcined alumina / magnesia composite oxide catalyst is a catalyst obtained by calcining the catalyst represented by the formula (2) or the hydrotalcite represented by (3) at 400 to 950 ° C. for 0.5 to 12 hours. The manufacturing method of any one of Claims 1-5:
nMgO.Al ₂ O ₃ · mH ₂ O (2)
(N is a number from 2 to 18, and m is a number from 0 to 20)

[Mg ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^{X +} [A ^n-1 _{x / n} · mH ₂ O] ^x- (3)
(0.1 ≦ x ≦ 0.5, and ^An-1 is selected from CO ₃ ²⁻ , SO ₄ ⁻² , OH ⁻ , NO ₃ ⁻ , Fe (CN) ₆ ³⁻ or CH ₃ COO ^−. And m is 0-20.)   Fatty acid polyoxy prepared by treating a calcined alumina-magnesia composite oxide catalyst with a basic substance selected from alkali metal carbonates, silicates and carboxylates, organic amines having a molecular weight of less than 1000 and quaternary salts thereof. Catalyst for the production of alkylene alkyl ethers.