KR101874024B1 - Manufacturing method of amino acid-based surfactant - Google Patents

Abstract

The present invention relates to a process for producing an amino acid surfactant, and more particularly, to a process for producing an amino acid surfactant, which comprises the steps of: preparing an amino acid surfactant having excellent physical and chemical properties such as solubility in water, It is possible to provide a production method capable of mass production.

Description

[0001] The present invention relates to an amino acid-based surfactant,

The present invention relates to a method for producing an amino acid-based surfactant, and a method for producing an amino acid-based anionic surfactant having excellent biodegradability and solubility in water.

Surfactants are compounds that have both a hydrophilic group and a lipophilic group in one molecule and exist in a natural system or are made by synthesis, and there are tens of thousands kinds. Surfactants have functions such as emulsification, solubilization, dispersion, washing, wetting, bubbling, antistatic, and sterilizing. They are used in detergents, fibers, cosmetics, medicines, foods, paints, pesticides, paper, mining, lubricants, Shafts, rubber, plastics, petroleum, and soil regeneration. In particular, household and industrial detergents used for hygiene and cleaning purposes contain a surfactant as a main component and play a key role in cleaning. In order for surfactants to be used in household and industrial detergents, various requirements must be met. That is, since the detergent is used in a large amount due to its nature of use, and the price is relatively low, the surfactant used therein must also be mass-produced at an economical cost. In addition, the detergent may come into contact with the human body during use, and since it is discharged through sewage together with water after use, it should not cause toxicity and irritation when it comes in contact with and absorbed by human body. And the natural ecosystem, the impact on the water environment should be small.

In recent years, attempts have been made to develop surfactants in terms of basic performance, economical efficiency, safety for human body and environment, and saving resources and energy.

Thus, the present applicant has succeeded in minimizing the production of unreacted materials with high reactivity by using high-level alcohol derived from amino acid materials and natural oils that are present in the natural environment, and is environmentally and humanly safe and biodegradable The present inventors have found that an amino acid type anionic surfactant which is not only excellent but also has improved interfacial properties can be prepared and the present invention has been completed in order to provide a method for producing the same.

An object of the present invention is to provide a method for producing an amino acid-based anionic surfactant which exhibits excellent solubility even at a low temperature, and which has very low irritation to human body and excellent interfacial properties.

To this end, the method for preparing an amino acid surfactant according to the present invention provides a step of subjecting a triglyceride derivative to a chlorinated addition reaction and then reacting with an amino acid. At this time, the step is performed at 0 to 20 ° C, and the following pH condition is satisfied.

12 ≤ pH ≤ 14

According to one embodiment of the present invention, the amount of the amino acid to be used is not limited, but it is preferable that the amino acid is used in the range of 1.0 to 2.0 mol based on 1 mol of the triglyceride derivative.

According to one embodiment of the present invention, the triglyceride derivative is selected from the group consisting of shea butter, cucumber butter, mango butter, pitch butter, lime butter, argan butter, jojoba butter, coffee butter, cocoa butter, pasta chew butter, One or more triglycerides selected from Lanolin Butter, Olive Butter, Camellia Butter, Aloe Vera, Vanilla Butter, Avocado Butter, Sami Butter, Ilreif Butter, Coombe Butter, Mocha Chino Butter, Mururuvur Butter, Shea Aloe Butter and Sweet Almond Butter Containing material, and imparts an affinity to the amino group of the amino acid. At this time, the amino group of the amino acid may be one or two, and is characterized by having at least one lipophilic group always attached from the fatty acid compound.

According to an embodiment of the present invention, the reaction may be carried out using triglyceride derivative as a solvent, and further, one or more lower alcohols selected from methanol, ethanol, propyl alcohol, isopropyl alcohol, The reaction can be carried out.

According to one embodiment of the present invention, the chlorination addition reaction may be carried out by charging at least one acylating agent selected from phosphorus trichloride, phosphorus trichloride, and sulfosuccinic chloride.

According to an embodiment of the present invention, the step of neutralizing the product obtained in the above step may further include the step of producing an alkali salt, wherein the step of producing the alkali salt is followed by vacuum distillation to concentrate the product . The concentration of the amino acid surfactant according to the present invention may be concentrated to a solid content of 20 to 90% by weight, but the content is not limited thereto.

According to the present invention, not only mass production is possible in a very economical manner, but also the remaining of unreacted materials with a high reactivity is minimized and a complicated purification process is not necessary. In addition, since the used solvent can be reused by vacuum distillation, environmental pollution is small.

In addition, the amino acid surfactants prepared therefrom have excellent physico-chemical properties such as solubility in water, foaming power, detergency and biodegradability, and can be used as a substitute for synthetic surfactants used in conventional industrial fields And it is expected to be applied in a wide range of fields, such as cosmetics, soaps, detergents, and shampoos, which are in contact with the human body because of low irritation to the human body.

1 is a ¹ H-NMR spectrum of an amino acid surfactant according to Example 1,
2 is a ¹³ C-NMR spectrum of the amino acid surfactant according to Example 1. Fig.

The method for producing the amino acid surfactant according to the present invention will be described below. However, unless otherwise defined in the technical terms and scientific terms used herein, it is to be understood that those skilled in the art In the following description, well-known functions and constructions that may unnecessarily obscure the gist of the present invention will not be described.

The present invention provides a method for producing an amino acid-based surfactant comprising the step of subjecting a triglyceride derivative to a chlorinated addition reaction followed by reaction with an amino acid. At this time, the step according to the present invention may satisfy the following reaction conditions.

0 ° C ≤ P _Temp ≤ 20 ℃

12 ≤ pH ≤ 14

According to one embodiment of the present invention, it is possible to provide a saccharide-based surfactant in a very economical manner since it is possible not only to minimize the residual of unreacted materials with high reactivity, can do.

The triglyceride derivative according to an embodiment of the present invention may be selected from the group consisting of shea butter, cucumber butter, mango butter, pitch butter, lime butter, argan butter, jojoba butter, coffee butter, cocoa butter, pasta chew butter, rice butter, One or more natural triglycerides selected from butter, olive butter, camellia butter, aloe butter, vanilla butter, avocado butter, sammi butter, sun leaf butter, coccum butter, mocha chino butter, mulmu butter, shea aloe butter and sweet almond butter In the case of a triglyceride derivative obtained from shea butter, jojoba butter, cocoa butter, olive butter, shea aloe butter and the like, which can be obtained from a ceramide-containing substance and contains a saturated or unsaturated fatty acid having 8 to 18 carbon atoms as a main component, Not only does it show high reactivity with amino acids, but also the amino acid-based interface The stabilizer is preferred because it has excellent foam stability. In particular, the triglyceride derivative obtained from cocoa butter has surprisingly improved interfacial properties, but the present invention is not limited thereto. At this time, the triglyceride compound obtained from the natural triglyceride-containing substance may be a single substance or a mixture, but when it is a mixture, it is possible to realize a more preferable effect on the interfacial property, Can be minimized.

The triglyceride derivative according to an embodiment of the present invention may preferably include a triglyceride derivative represented by the following formula (1).

[Chemical Formula 1]

[Chemical Formula 1]

R ₁ to R ₃ are each independently (C 8 -C 30) alkyl or (C 8 -C 30) alkenyl]

The "step of reacting the triglyceride derivative with the amino acid after the chlorinated addition reaction" described in the present invention is hereinafter referred to as a "condensation reaction step" so as to be distinguished from the additional reaction step.

The "triglyceride derivative" described in the present invention may be a single substance or a mixture. In addition, the triglyceride derivatives obtained from natural ingredients have triglycerides of a specific structure as main components, though they are mostly in a mixture state. Here, the main component means a component corresponding to not less than 70% by weight based on the total weight of the mixture.

The term " alkyl "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. In addition, when the fatty acid compound according to the present invention has hydrocarbons having 8 to 18 carbon atoms, carbon hydride having a carbon number of more than 18 is preferred because it has superior bubble power, stability of bubbles and washing power without affecting lowering of solubility in water. The present invention is also included as an aspect of the present invention.

According to an embodiment of the present invention, R ₁ to R ₃ of the triglyceride derivative may simultaneously be (C 8 -C 18) alkyl or (C 8 -C 18) alkenyl, and have high solubility in water, R ₁ to R ₃ are preferably (C 8 -C 18) alkyl at the same time from the viewpoints of excellent workability and usability due to their low viscosity even when used at a high concentration.

According to one embodiment of the present invention, in the chlorination addition reaction, any chlorinating agent may be used without limitation, and as a preferable example thereof, at least one selected from phosphorus trichloride, phosphorus trichloride, The acylating agent added in an excess amount can be easily removed by volatilization by vacuum distillation, and phosphorus trichloride is more preferably used in view of excellent reactivity in the chlorination addition reaction. At this time, the chlorination addition reaction is carried out without any additional solvent, and glycerol (C ₃ H ₅ (OH) ₃ ), phosphorous acid (H ₃ PO ₃ ) And can be easily removed after the reaction.

According to an embodiment of the present invention, the amount of the acylating agent used in the chlorination addition reaction is not limited, but may be in the range of 1.0 to 2.0 mol based on 1 mol of the triglyceride derivative. But it may be used in the range of 1.0 to 1.5 mol in view of minimizing impurities due to unreacted materials within a range not affecting reactivity, but is not limited thereto.

According to one embodiment of the present invention, the chlorinated acyl compound produced from the triglyceride derivative by the chlorination addition reaction is condensed with various amino acids to have high reactivity, and is excellent in biodegradability and hypoallergenic properties to human body Active agent. The amino acid may be selected from the group consisting of valine, leucine, isoleucine, threonine, methionine, lysine, phenylalanine, tryptophane, glycine, , Alanine, glutamic acid, L-arginine, cystine, cysteine, proline, serine, tyrosine, asparagine, ), Aspartic acid, histidine and derivatives thereof, and a preferable example from the viewpoint of the physical properties of the final product, particularly in view of high solubility in water and improved interfacial properties, is glycine (glycine), glutamic acid, arginine (L-arginine), and derivatives thereof, but is not limited thereto.

The condensation reaction step according to an embodiment of the present invention may be used in the range of 1.0 to 2.0 moles of the amino acid based on 1 mole of the triglyceride derivative. At this time, when the amino acid was used in the range of 1.0 to 1.3 mol per 1 mol of the triglyceride derivative, the reaction yield was in the range of 60 to 70%, but for whatever reason, the use of more than 1.3 mol of amino acid within the above- It was confirmed that the reaction yield was remarkably improved to 90% or more. In particular, when an amino acid of 1.3 to 1.7 moles is used, high-yield characteristics are exhibited, and the present invention is not limited thereto.

The condensation reaction step according to an embodiment of the present invention is not limited as long as it is a temperature not higher than room temperature (23 ° C), but may be carried out under mild conditions, preferably 0 to 20 ° C, RTI ID = 0.0 > 20 C. < / RTI > If the temperature is outside the reaction temperature range described above, denaturation of the amino acid occurs, which may result in problems such as color change, odor generation, and the like.

In addition, it was found that the pH control during the reaction was a key factor in the condensation reaction step according to an embodiment of the present invention. A high exothermic reaction occurs during the reaction and the acidity of the pH is increased. It is preferable to further include a step of adding base and adjusting the pH to maintain the above-mentioned pH range by such a phenomenon.

The condensation reaction step according to an embodiment of the present invention is preferably carried out in at least one reaction solvent selected from methanol, ethanol, propyl alcohol, isopropyl alcohol and butyl alcohol. To prevent skin irritation, isopropyl alcohol But it is not limited thereto.

According to an embodiment of the present invention, the method may further include neutralizing the product obtained after the condensation reaction step to produce an alkali salt of the product. By alkali-chlorinating the product as described above, it is possible to reduce the odor peculiar to amino acids and effectively suppress the problems such as discoloration due to external environment such as heat, light and moisture, thereby improving the stability in storage such as long-term stability.

At this time, the base used in the step of generating the alkali salt is not limited but may be one or more selected from sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and the like.

According to an embodiment of the present invention, the step of producing the alkali salt of the product may further include a step of vacuum distillation to concentrate the product so that the solid content of the product becomes 20 to 90% by weight. From the viewpoint of reduction, it is preferable to concentrate to a solid content of preferably 20 to 50% by weight.

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.

In addition, the solubility, foaming power, biodegradability and irritability of the amino acid surfactants prepared by the following methods were evaluated in the following Tables 1 to 3 by performing the following methods.

1. Evaluation of solubility

The permeability of the amino acid surfactant prepared in Example 1 was measured using a TurbiScane LAb (Leanontech, pulse infrared light source; 880 nm). The transmittance was scanned at 37 ° C for 72 hours every 6 hours in the longitudinal direction of the sample solution, and the post-scattered (transmitted) light (135 °) was measured by the sample solution. As a control material, sodium lauryl ethyl sulfate sulfate (trade name: Sodium Lauryl Ether Sulfate 70, SLES) was diluted with 30 wt% aqueous solution and relative permeability was determined based on the permeability (1.0) .

2. Evaluation of bubble power

180 g of water was added to 20 g of the amino acid surfactant prepared in Example 1 to prepare a sample solution having a solid content of 3 wt%. After dropping 0.05 g of the artificial sebum solution, the rotation of the rotor was stopped by using a SITA R-2000 bubble analyzer (condition: rotated at 800 rpm / min 15 times (once for 20 seconds)), and then the height of the bubbles was measured. The mean value was obtained after repeated iteration.

3. Evaluation of biodegradability

OECD 301D Closed Bottle Test (OECD 301D Closed Bottle Test, test for 28 days to determine whether biodegradation is possible by 60% or more within two weeks from the start of decomposition of the sample) The final biodegradability of the amino acid surfactants prepared in Example 1 was evaluated. At this time, if the final biodegradability is more than 60%, it is judged that the biodegradability is excellent.

4. Evaluation of Irritability

And the HET-CAM method (Hen's Egg Chorioallantoic Membrane). 8: 2, 6: 4, 4: 6, 2: 8 and 0:10 by weight of a commercially available SLES 30 wt% aqueous solution and the amino acid surfactant prepared in Example 1 (30 wt% Were prepared and evaluated for their irritancy. The criteria for evaluation were unstimulated (0), light stimulus (1), moderate irritation (2), erythema with edema (3) It was evaluated as strong erythema accompanied by (4).

(Example 1)

Stage 1;

660 g (1 mole, product name: CNO oil) of triglyceride derivative derived from cocoa butter was added to a 1 L four-necked flask reactor equipped with a stirrer, a thermometer and a distiller equipped with a condenser, 151.06 g (1.1 mole) of phosphorus trichloride was gradually added thereto. After the addition of phosphorus trichloride was completed, the mixture was stirred for 6 hours. After completion of the reaction for 6 hours, stirring was stopped while maintaining the temperature of the reactor, glycerol and phosphorous acid as side products were removed from the bottom of the reactor, and vacuum was applied to remove remaining phosphorus trichloride (670.11 g yield = 99.38%). It was then used in the next reaction without further purification.

Step 2;

A 1-L 5-neck flask reactor equipped with a stirrer, a thermometer and a condenser was charged with 450 g of ionized water, 75.07 g (1.4 mole) of glycine, 140 g of KOH (40 wt% in H ₂ O) (PH 12.5). The reaction temperature was kept at 15 ° C, and 222.36 g (1 mol) of the product prepared in the above step 1 was gradually added to the reaction solution to confirm the pH change (pH maintenance of the reaction solution was the key). At this time, NaOH (50 wt% in H ₂ O) was further added during the reaction to maintain the pH of 12.5 because the pH was decreased along with the exothermic reaction as the product prepared in the above step was added. After completion of the addition of the product prepared in Step 1, the reaction was carried out at the same temperature for 6 hours. After the reaction was completed, the reactor was sealed, heated to 60 ° C and vacuumed to remove the isopropyl alcohol as a reaction solvent to obtain an amino acid surfactant having a solid content of 30 wt% (in H ₂ O, C ₁₄ H ₂₆ NNaO ₃ , Mol. Wt .: 279.35).

Structural analysis (NMR) data of the amino acid surfactants prepared by the above method are as follows (see FIGS. 1 and 2).

1H-NMR (400 MHz, CD 3 OD): δ 4.893 (s, 1H), 3.721 (s, 2H), 2.234 (t, 2H), 1.610 (br, 2H), 1.262 (br, 18H), 0.893 ( t, 3H)

13 C-NMR (400 MHz, CD ₃ OD): δ 176.817, 176.011, 49.787, 49.575, 49.362, 49.937, 48.724, 48.512, 44.738, 37.321, 33.224, 30.916, 30.798, 30.659, 30.630, 30.571, 27.031, 23.887, 14.616

(Example 2-10)

The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1 below to obtain an amino acid-based surfactant (in H ₂ O) having a solid content of 30 wt%.

In addition, the solubility, the foaming power and the biodegradability of the amino acid surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

(Comparative Example 1-4)

The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1 below to obtain an amino acid-based surfactant (in H ₂ O) having a solid content of 30 wt%.

In addition, the solubility, the foaming power and the biodegradability of the amino acid surfactant prepared by the above method were evaluated by the method in Example 1 and shown in Tables 1 and 2 below.

As can be seen from Tables 2 and 3, according to the present invention, not only high solubility in water but also bubble power equal to or higher than that of a conventional surfactant can be realized and high cleaning power can be provided. Also, according to the present invention, it is possible to provide an anionic surfactant which is low in irritation to human body and excellent in biodegradability.

In addition, according to the present invention, the amino acid surfactant having the above-mentioned excellent properties can be provided in a more competitive and eco-friendly manner by minimizing the residual of unreacted materials with high reactivity and performing a mild reaction process that does not require a complicated purification process can do.

Claims (7)

Reacting the triglyceride derivative with chlorine and then reacting with glycine, wherein the glycine is used in the range of 1.4 to 1.7 mol based on 1 mol of the triglyceride derivative and is performed at 0 to 20 DEG C , And the following pH conditions are satisfied.
12 ≤ pH ≤ 14 delete The method according to claim 1,
The triglyceride derivatives may be selected from the group consisting of shea butter, cucumber butter, mango butter, pitch butter, lime butter, argan butter, jojoba butter, coffee butter, cocoa butter, pasta chew butter, rice butter, vegetable lanolin butter, Which is obtained from at least one triglyceride-containing material selected from aloe butter, vanilla butter, avocado butter, sammi butter, ilefree butter, coccum butter, mocha chino butter, mullum butter, shea aloe butter and sweet almond butter. A method for producing a surfactant. The method according to claim 1,
Wherein the chlorination addition reaction is carried out by introducing at least one selected from phosphorus pentachloride, phosphorus trichloride and sulfosuccinic chloride. The method according to claim 1,
Wherein the step is carried out in at least one reaction solvent selected from methanol, ethanol, propyl alcohol, isopropyl alcohol and butyl alcohol. The method according to claim 1,
And neutralizing the product obtained in the above step to produce an alkali salt. The method according to claim 6,
Further comprising the step of concentrating the product so as to have a solid content of 20 to 90% by weight by vacuum distillation after the step of producing the alkali salt.

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