WO2013017222A1 - Procédé de préparation de monoalcanolamide d'acide gras - Google Patents

Procédé de préparation de monoalcanolamide d'acide gras Download PDF

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Publication number
WO2013017222A1
WO2013017222A1 PCT/EP2012/003155 EP2012003155W WO2013017222A1 WO 2013017222 A1 WO2013017222 A1 WO 2013017222A1 EP 2012003155 W EP2012003155 W EP 2012003155W WO 2013017222 A1 WO2013017222 A1 WO 2013017222A1
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Prior art keywords
reaction
fatty acid
temperature
water
carried out
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PCT/EP2012/003155
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English (en)
Inventor
Hideo Takeuchi
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Clariant International Ltd
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Publication date
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Publication of WO2013017222A1 publication Critical patent/WO2013017222A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the present invention relates to a process for preparing a fatty acid
  • monoalkanolamide and particularly relates to a process for preparing a fatty acid monoalkanolamide having low odor and low color, which contains an extremely small amount or substantially no amount of impurities such as ester amines, amide esters, and cyclic amines.
  • Fatty acid monoalkanolamides are used in cleaning agents for kitchen, and cosmetic cleaning agents for skin or hair (body soaps, hair shampoos), or the like as chemicals which contribute to improvement in the thickening, foam stability and detergency of the cleaning agents.
  • monoalkanolamines it is general to carry out a reaction by mixing and heating the fatty acids and monoalkanolamines and carry on the reaction under the removal of the water formed during the reaction from the system by distillation or the like. This is because the reaction is a dehydrating and condensation reaction.
  • monoalkanolamines have two reaction sites capable of reacting with fatty acids in the single same molecule, that is, amine and alcohol moieties.
  • ester amine (2) fatty acid ester amines
  • amide ester (3) monoalkanolamide esters
  • JP4079470B is characterized in that 1.0 to 1.3 moles of a monoalkanolamine are added to a fatty acid in two stages; in particular, in the first stage, 0.8 to 0.95 moles of a monoalkanolamine is reacted to prepare a mixture composed mainly of an alkanolamide and an amide ester, and then in the second stage, the remaining monoalkanolamine is added to the reaction product from the first stage to convert the amide ester to an alkanolamide.
  • the desired product amide and the by-product amide ester are formed by carrying out the reaction at a temperature of 150 to 160 °C under the removal of the resulting water from the system.
  • the conversion rate needs to be increased by using a sodiummethylate- methanol solution as a catalyst.
  • a sodiummethylate- methanol solution as a catalyst.
  • the use of an organic solvent requires the removal of the organic solvent from the system after the completion of the reaction, in particular, in respect to methanol, the safety standard "must not be detected from products" is present in quality standards for household products and standards for cosmetics, and therefore, the use of such a substance poses a problem.
  • JP09157234A is characterized in that a fatty acid and an alkanolamine are added in two stages, wherein, in the first stage, 0.6 to 0.95 mole of an alkanolamine is added to a fatty acid and reacted for 1 to 8 hours, and then in the second stage, the remaining alkanolamine is reacted in the absence of a catalyst for 1 to 8 hours.
  • the reaction temperature is 130 to 200 °C.
  • Claim 4 recites that the reaction is carried out under a reduced pressure, or it is described in Examples that the reaction was carried out in a nitrogen stream; namely there is disclosed a process wherein the reaction is carried out under the removal of the water formed during through the reaction from the system.
  • reaction temperature is 150 °C or more
  • the formation rate of ester amines is promoted, further associated with the formation of by-products such as cyclic amines, thereby leading to a low purity of the desired product.
  • a basic catalyst such as sodium hydroxide and sodium methoxide and thereby prevent the formation of impurities such as cyclic amines; however, the treatment of the alkali formed from the alkali catalyst, and of the solvent, is problematic.
  • the methanol formed therefrom is classified as a substance which must not be detected, in quality standards for household products and standards for cosmetics and therefore, the use of sodium methoxide is hesitated.
  • the formation of a by-product, a cyclic amine occurs when promoting the removal of water from the reaction system in such conditions that the amine is excessive relative to the fatty acid and the temperature is 130 °C or more.
  • An object of the present invention is to provide a process for effectively preparing a fatty acid monoalkanolamide comprising an extremely small amount or substantially no amount of impurities such as ester amines, amide esters, and cyclic amines without requiring the presence of a basic catalyst and an organic solvent.
  • a further object of the present invention is to provide a fatty acid
  • a still further object of the present invention is to provide a fatty acid
  • the reaction does not require the presence of a basic catalyst and an organic solvent and further, even if the water formed during the reaction is not removed, the formation rate of the desired product fatty acid monoalkanolamides does not alter compared to the reaction where the water is removed by means of a nitrogen stream or distillation, and the formation rate of the amides is higher at a higher temperature.
  • the present inventor has found the fact that the removal of water by means of a nitrogen stream or under a reduced pressure at a high temperature exceeding 150 °C promotes the formation of ester amides or cyclic amides and gives an amide comprising by-products in a high amount; in contrast thereto, in the case of a reaction in a system where water is present, the formation of cyclic amine derivatives and the like is very low, further the contents of ester amines and amide esters formed are also extremely low, and therefore, the desired product is obtained in high purity.
  • the amine odor of the product it has also been found that, if water is added to a reaction mixture after the completion of the reaction, which comprises the final product, and the remaining monoalkanol amine is
  • the temperature during the reduced-pressure distillation is set to 125 °C or less, then the remaining monoalkanol amine can be successfully removed, while
  • the present inventor assumed that the coloration of the final product would be due to the oxidation of the amine and has tried applying various types of reducing agents, and as a result has found that reducing agents of an inorganic salt type such as, for example, sodium sulphite, are not soluble in the final product amide, thus causing turbidity of the molted solution and, on the other hand, even in the case of reducing agents soluble in fats and oils components, no effect can be achieved with hypophosphorous acid; however, significant suppression of coloration can be first achieved using reducing organic acids, and products having a good color hue can be obtained.
  • an inorganic salt type such as, for example, sodium sulphite
  • the present invention relates to;
  • Figure 1 is a gas chromatograph of a fatty acid monoalkanolamide obtained according to the present invention (Example 3).
  • Figure 2 is a gas chromatograph of a fatty acid monoalkanolamide obtained by carrying out a reaction with removal of water from the reaction system, according to the prior art (Comparative Example 1).
  • the fatty acid used according to the present invention is preferably represented by the following formula (1).
  • R 1 represents a linear or branched alkyl, alkenyl or hydroxyalkyl group having 5 to 21 carbon atoms.
  • the fatty acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, nonadecanoic acid, behenic acid, erucic acid, and 12-hydroxystearic acid; and a vegetable or animal oil fatty acid such as coconut oil fatty acid, cotton seed oil fatty acid, corn oil fatty acid, tallow fatty acid, babassu fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid, and whale oil fatty acid.
  • Particular preference is given to caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
  • the monoalkanolamine, a further reactant used according to the present invention is preferably represented by the following formula (2).
  • R 2 represents a hydrogen atom, or a linear or branched alkyl or hydroxyalkyl group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms.
  • R 3 represents a linear or branched alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
  • R 2 examples include a hydrogen atom, a hydroxyethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and a 2-ethylhexyl group.
  • R 2 is a hydrogen atom.
  • R 3 examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, and a hexylene group.
  • R 3 is an ethylene group.
  • Examples of the monoalkanolamine represented by the formula (2) include monoethanolamine, diethanolamine, isopropanolamine, N-methylethanolamine, N-methylisopropanolamine, N- ethylethanolamine, and N-ethylbutanolamine, and preferably include
  • the reaction between the fatty acid and the monoalkanolamine is carried out at a temperature of 140 to 170 °C, preferably of 150 to 170 °C. Even if the
  • the reaction is carried out in the presence of a certain appropriate amount of water unlike the prior art process where the reaction is carried out under the removal of the water formed.
  • the removal of water is not necessary as long as a temperature of 140 °C or more can be maintained, but, if an amount of water sufficient for suppressing the formation of by-products can be kept in the reaction system, the water may be removed continuously or discontinuously during the reaction. This is what the description "without substantially removing" means. In this manner, it is possible to suppress the formation of by-products such as ester amines, amide esters, and cyclic amines.
  • the desired amide, and the amide ester, ester amine and cyclic amine are presumed to form in respective formation rates in this order and, in this case, the presence of an appropriate amount of water inhibits the formation of the by-product ester or hydrolyzes the ester once formed, and also inhibits the occurrence of inter- molecular dehydrating condensation leading to the formation of the cyclic amine.
  • Remaining fatty acid 2.0 % by weight or less
  • Ester amide 1.0 % by weight or less
  • Amide ester 1.0 % by weight or less
  • the reaction may be carried out in the presence of a basic catalyst such as sodium hydroxide and sodium methoxide.
  • a basic catalyst such as sodium hydroxide and sodium methoxide.
  • it is advantageously possible to dispense with basic catalysts without increasing the amounts of by-products formed even at a relatively high temperature of 140 to 170 °C by means of allowing a certain amount of water to exist during the reaction.
  • the reaction can go without the use of additional chemicals and the removal operation of such additional chemicals, which provides an advantage in view of cost.
  • sodium methoxide is a substance which may form methanol classified as a substance which must not be detected in quality standards for household products and standards for cosmetics.
  • the process according to the present invention does not require such a basic catalyst, and therefore, has a particular feature that there is no need to consider the possibility that methanol originating from the preparation remains in the final product.
  • the reaction may be carried out in the presence of an organic solvent, while the presence of an organic solvent is not essential.
  • organic solvents have a risk of, due to the fact that they usually have a boiling point lower than that of water, inhibiting the refluxing of water and preventing the reaction temperature from raising to a desired temperature; and also have the problem that, even in the case of organic solvents having a boiling point higher than that of water, the removal thereof is difficult.
  • handling of organic solvents is associated with fire or explosion hazards. Therefore, it is
  • the reaction is carried out at a temperature of more than 150 °C, for example, at a temperature of 160 to 170 °C, the formation of by-products can be suppressed, and further the reaction time can be shortened to about 1/2 of that of the reaction at 150 °C and nevertheless, the desired amide can be obtained with a comparable or higher level of purity.
  • the fatty acid and the monoalkanolamine are reacted with each other by using, relative to the fatty acid, an equivalent amount or a molar excess amount of the monoalkanolamine.
  • the molar ratio of the monoalkanolamine per mole of the fatty acid is preferably 1.0 to 1.5 moles, and particularly preferably 1.0 to 1.3 moles. If the mole ratio is less than 1.0 mole, the amount of the fatty acid is excessive, and such an excessive unreacted fatty acid remains in the final product, which leads to a decrease in purity.
  • the monoalkanolamine may be used in an amount more than 1.5 moles relative to the fatty acid, without influencing the purity, but it would require distilling off a higher amount of unreacted monoalkanol amines after the completion of the reaction and thus be not preferable from economical viewpoint.
  • the reaction between the fatty acid and the monoalkanolamine is carried out in the presence of a reducing organic acid.
  • the reaction product is sometimes colored due to an oxidized product derived from the amine.
  • the amount of the reducing organic acid is generally 50 to 200 ppm by weight, preferably 50 to 100 ppm by weight relative to the total amount of the monoalkanolamine and the fatty acid. If the amount is less than 50 ppm, sufficient oxidation-suppressing effects cannot be expected. On the other hand, if the amount exceeds 200 ppm, the reducing organic acid may react with and consumes the amine which should have been available to the formation of the desired amide, and the product formed from such a reaction is a by-product, which leads to a decrease in purity of the final product. Examples of the reducing organic acid particularly include oxalic acid, formic acid, and ascorbic acid.
  • the unreacted monoalkanolamine remaining after the reaction can be removed by distillation under a reduced pressure, if necessary.
  • water may be added to the reaction mixture and then subjected to reduced-pressure distillation.
  • the ester moiety in the by-product amide ester is hydrolyzed to form the desired amide, thereby further improvement in purity can be achieved.
  • the monoalkanolamine which may still remain, is distilled off by azeotropic distillation with water, thereby yet further improvement in purity and further reduction of odor originating from the monoalkanolamine can be achieved.
  • the conditions for this distillation are a temperature of 125 °C or less and a reduced pressure (for example, 100 to 3 Kpa/water pump at the beginning, and then, 1 Kpa or less/dry pump, for example, 0.1 to 0.3 Kpa/dry pump).
  • a temperature exceeding 125 °C may promote intermolecular dehydrating cyclization and lead to the formation of by-products.
  • the reaction between the fatty acid and the monoalkanolamine can be carried out in the presence of a heavy metal amidation catalyst, for example, in the presence of at least one metal compound selected from compounds of chromium, manganese, iron, cobalt, nickel, hafnium, indium, copper, zinc, magnesium, calcium, aluminum, and lithium.
  • a heavy metal amidation catalyst include a halide such as chloride and bromide; a sulphate, a nitrate, a phosphate, a perchlorate; a carboxylate such as acetate, chloroacetate, trifluoroacetate, and acetylacetate; and an oxide of the aforementioned metals.
  • the heater temperature was set at 160 °C, and then, the distillation line was opened and the reaction water was discharged by atmospheric distillation until the temperature of the reaction mixture rose to 158 °C. After that, the distillation line was closed to get back to refluxing. Further, at 1 hour, 2 hours, and 4 hours after the beginning of the reaction, analogously, the distillation line was opened and atmospheric distillation was carried out, and then refluxing was recovered again. At 12 hours after the beginning of the reaction, heating was stopped, and the reaction mixture was cooled to 90 °C and then subjected to distillation under a reduced pressure.
  • the distillation line was opened and the reaction water was discharged by atmospheric distillation until the temperature of the reaction mixture rose to 167 °C. After that, the distillation line was closed to get back to refluxing. Further, at 40 minutes, 1 hour, and 2 hours after the beginning of the reaction, analogously, the distillation line was opened and atmospheric distillation was carried out, and then refluxing was recovered again and the reaction was continued. At 7 hours after the beginning of the reaction, heating was stopped, and the reaction mixture was cooled to 90 °C and then subjected to distillation under a reduced pressure.
  • the distillation line was opened, and the reaction water was discharged by atmospheric distillation until the temperature of the reaction mixture rose to 167 °C. After that, the distillation line was closed to get back to refluxing. Further, at 40 minutes, 1 hour, and 2 hours after the beginning of the reaction, analogously, the distillation line was opened and atmospheric distillation was carried out, and then refluxing was recovered again and the reaction was continued. At 7 hours after the beginning of the reaction, heating was stopped, the reaction mixture was cooled to 90 °C and then subjected to distillation under a reduced pressure.
  • the temperature was set at 150 °C and reduced-pressure distillation was carried out. Thereafter, the following operation was repeated three times. That is, after the addition of 5 g of water and subsequent stirring, reduced-pressure distillation was carried out using a water pump instead, and then reduced-pressure distillation was carried out using a dry pump then until the temperature was 120 °C. After the operation, the product thus obtained was poured onto an aluminum foil, and the cooled and solidified product was subjected to GC analysis.
  • the distillation line was opened and the reaction water was discharged by atmospheric distillation until the temperature of the reaction mixture rose to 178 °C. Thereafter, the distillation line was closed to get back to refluxing. Further, at 40 minutes, 1 hour, and 2 hours after the beginning of the reaction, analogously, the distillation line was opened and atmospheric distillation was carried out, and then refluxing was recovered again and the reaction was continued. At 5 hours after the beginning of the reaction, heating was stopped, and the reaction mixture was cooled to 90 °C and then reduced-pressure distillation was carried out.
  • the residual content of the fatty acid was small (i.e., high reaction efficiency) and, further, it was possible to suppress the contents of the by-products to very low levels. In addition, the peculiar odor of the final product was slight.
  • Examples 1 - 3 shows that, in this case, while suppressing the contents of the fatty acid and the by-products to low levels, it was possible to shorten the reaction time almost half of those in Examples 1 to 3. Again, the peculiar odor of the final product was slight.
  • Example 5 which, compared to Examples 1 to 3, was carried out at a higher temperature and without azeotropic distillation by the addition water after the completion of the reaction, it was possible to reduce the content of the remaining fatty acid to a low level of .31 % already after 6.5 hours and, moreover, the amounts of the by-products formed were sufficiently satisfactory levels. In this example, however, a strong ammonium odor remained in the final product. This ammonia odor could be improved by adding water to the reaction mixture, followed by distillation.
  • Comparative Example 1 which was carried out a relatively high temperature (160 °C) while continuously discharging the water from the reaction system, a very large amount of the by-product amide ester formed 12 hours after the beginning of the reaction (the content of the remaining fatty acid: 1.1 %).
  • the amounts of the other by-products formed were also higher than the examples according to the present invention.
  • the final product emitted a strong ammonia odor.
  • Comparative Example 3 was carried out under refluxing the water analogously to the inventive examples, but at a higher reaction temperature of 170 to 180 °C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un monoalcanolamide d'acide gras, contenant une quantité extrêmement petite ou pratiquement aucune quantité d'impuretés comme des amines d'ester, des esters d'amide et des amines cycliques, sans nécessiter l'utilisation d'un catalyseur basique ni d'un solvant organique. L'invention a donc pour objet un procédé de préparation d'un monoalcanolamide d'acide gras en faisant réagir un acide gras avec une monoalcanolamine, dans lequel, par rapport à l'acide gras, une quantité équivalente ou une quantité en excès molaire de la monoalcanolamine est mise à réagir à une température de 140 à 170 °C, et la réaction est réalisée en présence d'eau sans pratiquement éliminer l'eau résultante du système réactionnel tant qu'il est possible de maintenir la température de la réaction dans la plage de 140 à 170 °C.
PCT/EP2012/003155 2011-08-02 2012-07-26 Procédé de préparation de monoalcanolamide d'acide gras WO2013017222A1 (fr)

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JP2011169500A JP5783839B2 (ja) 2011-08-02 2011-08-02 脂肪酸モノアルカノールアミドの製造方法
JP2011-169500 2011-08-02

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157234A (ja) * 1995-10-03 1997-06-17 Mitsui Toatsu Chem Inc 脂肪酸アルカノールアミドの製造方法
JPH09235258A (ja) * 1995-08-09 1997-09-09 Kao Corp モノアルカノールアミドの製造方法
US6017426A (en) * 1997-06-11 2000-01-25 L'oreal Process for the preparation of ceramide-type compounds
WO2008043493A1 (fr) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Procédé de production d'alcanolamides d'acides gras

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1252865B (it) * 1991-12-31 1995-06-28 Lifegroup Spa N-acilderivati di aminoalcooli attivi come autocoidi locali ed utilizzabili nella terapia dei processi autoimmuni
JP3503842B2 (ja) * 1995-05-01 2004-03-08 花王株式会社 アルカノールアミドの製造方法
JP2002037765A (ja) * 2000-07-25 2002-02-06 Kao Corp 高級脂肪酸アルカノールアミドの製造法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09235258A (ja) * 1995-08-09 1997-09-09 Kao Corp モノアルカノールアミドの製造方法
JPH09157234A (ja) * 1995-10-03 1997-06-17 Mitsui Toatsu Chem Inc 脂肪酸アルカノールアミドの製造方法
US6017426A (en) * 1997-06-11 2000-01-25 L'oreal Process for the preparation of ceramide-type compounds
WO2008043493A1 (fr) * 2006-10-09 2008-04-17 Clariant Finance (Bvi) Limited Procédé de production d'alcanolamides d'acides gras

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JP5783839B2 (ja) 2015-09-24

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