KR101894960B1 - A manufacturing method of biodegradable fatty acid-based surfactant - Google Patents
A manufacturing method of biodegradable fatty acid-based surfactant Download PDFInfo
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- KR101894960B1 KR101894960B1 KR1020150091096A KR20150091096A KR101894960B1 KR 101894960 B1 KR101894960 B1 KR 101894960B1 KR 1020150091096 A KR1020150091096 A KR 1020150091096A KR 20150091096 A KR20150091096 A KR 20150091096A KR 101894960 B1 KR101894960 B1 KR 101894960B1
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- following formula
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- 0 *C(NCCC[N+](*)(*)CC(COC(*)=O)O)=O Chemical compound *C(NCCC[N+](*)(*)CC(COC(*)=O)O)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
- A61K31/22—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin
- A61K31/221—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin with compounds having an amino group, e.g. acetylcholine, acetylcarnitine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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Abstract
The present invention relates to a process for producing a biodegradable fatty acid surfactant, and more particularly, to a process for producing a biodegradable fatty acid surfactant, which comprises reacting an amidopropylamine compound and a hydroxyester compound prepared from a fatty acid oil compound at a specific molar ratio, And a method for producing an eco-friendly fatty acid-based surfactant.
Description
The present invention relates to a process for producing a biodegradable fatty acid surfactant, and more particularly, to a process for producing an environmentally friendly fatty acid surfactant having excellent solubility in water and biodegradability.
Surfactants used in various industries have different properties depending on their application. Synthetic surfactant, which is generally used in the past, is easy to realize the HLB value according to the solubility in water and the intended use, and is used for cosmetic, pharmaceutical, metal processing, paper, paint, Has been used in various industrial fields such as textile, agriculture, construction and construction, food processing, cleaning, leather processing, etc. However, as the environmental pollution and the toxicity to the human body caused by this are strictly regulated, safety is high Development of an environmentally friendly surfactant having excellent biodegradability is urgently required.
Recently, a study on the development of an environmentally friendly surfactant for increasing biodegradability discloses that a biosurfactant is to be provided as a fermentation process of hydrocarbons using microorganisms in Non-Patent Document 001, Due to the problem of long and expensive facilities, commercialization has many difficulties.
Patent Document 001 discloses various phosphobetaine-structured compounds having an asymmetric structure. Patent Document 002 discloses quaternized cationic surfactants derived from triethanolamine. Patent Document 003 discloses a method for producing a poly Lt; RTI ID = 0.0 > cationic < / RTI > surfactants. However, in the case of a cationic surfactant having an ester bond as described above, solubility in water is very low, and in order to maintain product stability for a long time, a large amount of compounds such as glycerin, lower alcohols and nonionic dispersing agents must be used in a large amount, Not only the basic performance inherent to the active agent is deteriorated but also transparency is not ensured when dispersed. In the amidation or esterification reaction of fatty acids and amines disclosed in Patent Documents 001 to 003, there is a large amount of unreacted fatty acid after the reaction, a large amount of unreacted amine is present depending on the temperature condition, There is a problem that the amount of the synthetic amine of the amide-ester amine is large depending on the molar ratio of the quaternary agent such as halide and dimethyl sulfate, so that the purification process of the unreacted product is complicated and the complete removal is difficult to be performed.
Thus, the present applicant has found that an eco-friendly fatty acid surfactant having excellent biodegradability can be produced with high purity by a simple method of reacting an amide compound prepared from a fatty acid oil compound with a hydroxy ester compound, thereby completing the present invention.
It is an object of the present invention to provide a method for producing an environmentally friendly fatty acid-based bio-surfactant excellent in solubility and biodegradability in water.
For this purpose, the present invention provides a biodegradable fatty acid-based surfactant represented by the following formula (1) by reacting an amide propylamine compound represented by the following formula (2) and a hydroxy ester compound represented by the following formula And a manufacturing method thereof.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
[In formulas (1) to (4)
R 1 and R 2 are each independently (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl;
X < 1 > is halogen]
Also, the present invention provides a biodegradable fatty acid surfactant prepared by the above-described method and concentrated to have a solid content of 20 to 90% by weight.
The present invention is not only superior in solubility in water, but also superior in physico-chemical properties such as biodegradability and hypoallergenicness, thereby reducing environmental pollution by replacing a synthetic surfactant mainly used in existing industrial fields, It is expected that various industrial applications can be expected.
Also, the method of the present invention is economical and has an advantage that a high-purity biodegradable fatty acid surfactant can be easily provided.
The method for producing the biodegradable fatty acid surfactant according to the present invention will be described below. However, unless otherwise defined in the technical terms and scientific terms used herein, the person skilled in the art will understand In the following description, well-known functions and constructions which may unnecessarily obscure the gist of the present invention will not be described.
The present invention provides a process for preparing a biodegradable fatty acid surfactant represented by the following formula (1) by reacting an amide propylamine compound represented by the following formula (2) and a hydroxy ester compound represented by the following formula (3) .
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
[In formulas (1) to (4)
R 1 and R 2 are each independently (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl;
X < 1 > is halogen]
&Quot; Alkyl "as used in the present invention means a linear or branched hydrocarbon, and" alkenyl "means a linear or branched hydrocarbon having at least one double bond.
The fatty acid oil according to the present invention is preferably a fatty acid having a (C8-C20) alkyl group, and specific examples thereof include, but not limited to, vegetable oils such as coconut oil, rapeseed oil, cottonseed oil and palm oil.
The amadipropylamine compound of the following formula 2 according to an embodiment of the present invention may be prepared by condensation reaction of a fatty acid oil compound of the following formula 4 with an amine compound of the following formula 6, but is not limited thereto.
(2)
[Chemical Formula 4]
[Chemical Formula 6]
[In the formulas (2), (4) and (6)
R 2 is (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl]
In addition, the condensation reaction according to an embodiment of the present invention may include at least one acid catalyst selected from para-toluenesulfonic acid, phosphoric acid, hypophosphorous acid, sodium hypophosphite, and sulfuric acid; At least one base catalyst selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide; And at least one metal catalyst selected from iron (Fe), copper (Cu), cobalt (Co), titanium (Ti), tin (Sn) and manganese (Mn); But it is not limited thereto. It is preferable to use at least one catalyst selected from the above-mentioned acid catalyst in order to have more improved reactivity.
The condensation reaction according to the present invention can be carried out using 2.8 to 4 moles of the amine compound of the formula (6) based on 1 mole of the fatty acid oil compound of the formula (4), and the biodegradability And from the viewpoint of improving the stability of the fatty acid surfactant, it is preferable to use 3.2 to 3.5 moles.
In the condensation reaction according to the present invention, the catalyst may be used in an amount of 0.1 to 1.0 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the fatty acid oil compound of Formula 4, Can be good.
The condensation reaction may be carried out at a temperature of 100 to 200 ° C and may be carried out at a temperature of 150 to 180 ° C in order to smoothly perform the reaction and to minimize the unreacted materials and improve the transparency of the reactants.
The hydroxyester compound of Formula 3 according to the present invention may be prepared by reacting a fatty acid compound of Formula 5 with epihalohydrin, but is not limited thereto.
[Chemical Formula 5]
In Formula 5,
R < 1 > is (C1-C30) alkyl or (C2-C30)
The hydroxyester compound of Formula 3 according to the present invention may be prepared by using 1 to 2 moles of the epihalohydrin based on 1 mole of the fatty acid compound of Formula 5, preferably 1.2 to 1.5 It is better to use the mall.
The reaction of the hydroxy ester compound of formula (III) according to the present invention may be carried out at a temperature of 80 to 160 ° C, preferably at a temperature of 100 to 150 ° C.
The compound of Formula 1 according to an embodiment of the present invention may be prepared by using 1 to 1.5 moles of the amidopropylamine compound of Formula 2 based on 1 mole of the hydroxyester compound of Formula 3, It is preferable to use 1.1 to 1.2 moles.
In the preparation of the compound of Formula 1 according to an embodiment of the present invention, the reaction may be carried out at a temperature of 50 to 150 ° C, preferably at a temperature of 80 to 120 ° C.
In one embodiment of the present invention, the method for preparing the biodegradable fatty acid surfactant of Formula 1 may be embodied in the following Reaction Scheme 1, but is not limited thereto.
[Reaction Scheme 1]
[Reaction Scheme 1]
R 1 and R 2 are each independently (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl;
X < 1 > is halogen]
As shown in Reaction Scheme 1, the preparation method according to the present invention can provide a high purity biodegradable fatty acid-based surfactant even by a simple method. When the molar ratio of the reactants to a specific ratio of the reactants is as described above, And suppressing the occurrence of carbonization during the reaction, thereby producing a high-purity biodegradable fatty acid-based surfactant.
Also, the present invention provides a biodegradable fatty acid surfactant prepared by the above-described method and concentrated to have a solid concentration of 20 to 90% by weight.
The biodegradable fatty acid-based surfactant according to an embodiment of the present invention may be ideally concentrated to have a solid concentration of 20 to 50% by weight, and may be used for hair care, cosmetic composition, pharmaceutical composition, industrial antistatic agent, Cleaning compositions and the like.
Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto.
(Example 1-1)
(1 mole, molecular weight: 200.32 g) and NaOH (4 g) were added to a 1 L four-necked flask reactor equipped with a stirrer, a thermometer and a condenser, and the mixture was heated to 70 ° C to dissolve completely . 111.02 g (1.2 moles, molecular weight: 92.52 g) of epichlorohydrin was added dropwise to the mixture by dropwise addition for 1 hour while blowing in nitrogen of inert gas to prevent oxidation while stirring slowly, while avoiding contact with air. When epiklohydrin was added, the temperature inside the reactor was raised to 150 ° C and the reaction was allowed to proceed for 8 hours.
(Examples 1-2 to 1-16)
The hydroxy ester compound (Formula 3) was prepared in the same manner as in Example 1-1 except that the molar ratio of the fatty acid compound (Formula 5) and epihalohydrin was changed as shown in Table 1 below.
(Example 2-1)
(1 mole, molecular weight 672.6 g) of coconut oil, 1 g of hypophosphoric acid and 1 g of paratoluenesulfonic acid were put into a 1 L four-neck flask reactor equipped with a stirrer, a thermometer and a distiller equipped with a condenser , And completely dissolved by heating to 70 ° C. 357.6 g (3.5 moles, molecular weight: 102.18 g) of dimethylaminopropylamine was added dropwise at 190 ° C for 2 hours using a dropping device while nitrogen was blown into the reaction vessel to prevent oxidation, Respectively. Dimethylaminopropylamine was reacted for 6 hours after completion of the addition.
(Examples 2-2 to 2-11)
(2) was prepared in the same manner as in Example 2-1 except that the molar ratio of the fatty oil compound (Formula 4) and the amine compound (Formula 6) was changed as shown in Table 2 below, Respectively.
(Example 3-1)
292.77 g (1 mole, molecular weight 292.77 g) of the hydroxy ester compound (Formula 3) prepared in Example 1-1 and 312.93 g (1 mole) of the amidepropylamine compound (Formula 2) prepared in Example 2-1 mole, average molecular weight: 284.48 g) was charged into the reactor, and the reaction temperature was raised to 95 ° C and reacted for 10 hours.
(Examples 3-2 to 3-12)
(3), the type and molar ratio of the amide propylamine compound (2) were changed as shown in Table 3 below, and the biodegradable fatty acid-based interface Active agent.
Claims (13)
2) reacting an amide propylamine compound represented by the following formula (2) prepared from a fatty acid oil compound represented by the following formula (4) with a halo substituted ester compound represented by the following formula (3)
The method for producing a biodegradable fatty acid surfactant according to claim 1, wherein, in step 2), the amide propylamine compound is used in an amount of 1 to 1.2 mol based on 1 mol of the halo substituted ester compound.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[In the above formulas (1) to (5)
R 1 and R 2 are each independently (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl;
X < 1 > is halogen]
A process for producing a biodegradable fatty acid surfactant, wherein the amide propylamine compound of the following formula (2) is prepared by the condensation reaction of a fatty acid oil compound of the following formula (4) and an amine compound of the following formula (6).
(2)
[Chemical Formula 4]
[Chemical Formula 6]
[In the above formulas (2), (4) and (6)
R 2 is (C 1 -C 30) alkyl or (C 2 -C 30) alkenyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl]
Wherein the condensation reaction comprises at least one acid catalyst selected from para-toluenesulfonic acid, phosphoric acid, hypophosphorous acid, sodium hypophosphite, and sulfuric acid; At least one base catalyst selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide; And at least one metal catalyst selected from iron (Fe), copper (Cu), cobalt (Co), titanium (Ti), tin (Sn) and manganese (Mn); Wherein the method is carried out using at least one catalyst selected from the group consisting of:
Wherein the condensation reaction is carried out using 2.8 to 4 moles of the amine compound of the formula (6) based on 1 mole of the fatty acid oil compound of the formula (4).
Wherein the catalyst is used in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the fatty acid oil compound of formula (4).
Wherein the condensation reaction is carried out at a temperature of 100 to 200 ° C.
Wherein the halo substitution ester compound of Formula 3 is prepared by using 1 to 2 moles of the epihalohydrin based on 1 mole of the fatty acid compound of Formula 5. The present invention also provides a method for producing a biodegradable fatty acid-
Wherein the reaction is carried out at a temperature of from 50 to 150 ° C in the preparation of the compound of formula (1).
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| KR1020150091096A KR101894960B1 (en) | 2015-06-26 | 2015-06-26 | A manufacturing method of biodegradable fatty acid-based surfactant |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7186852B1 (en) | 2006-02-06 | 2007-03-06 | Rutherford Chemicals, Llc | Shea butter dimethyl amidopropyl amines |
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| US4283542A (en) | 1978-11-30 | 1981-08-11 | Mona Industries | Process for the preparation of phosphobetaines |
| ATE181956T1 (en) | 1992-05-12 | 1999-07-15 | Procter & Gamble | CONCENTRATED LIQUID FABRIC PLASTENER COMPOSITIONS WITH BIODEGRADABLE TISSUE PLASTICIZERS |
| DE4232448A1 (en) | 1992-09-28 | 1994-03-31 | Henkel Kgaa | Process for the preparation of powdered or granular detergent mixtures |
| KR100345192B1 (en) * | 1998-07-27 | 2002-07-24 | 주식회사 엘지생활건강 | Preparation of cationic surfactants containing ester group |
| KR20130000705A (en) * | 2011-06-23 | 2013-01-03 | 에이케이켐텍 주식회사 | A manufacturing method of phospholipids biosurfactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7186852B1 (en) | 2006-02-06 | 2007-03-06 | Rutherford Chemicals, Llc | Shea butter dimethyl amidopropyl amines |
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