TWI488688B - Preparation of green eultifunctional amino-acid type surfactant and its application - Google Patents

Description

Green and environmentally friendly multifunctional amino acid type surfactant, preparation method and application thereof

The present invention relates to an amino acid type surfactant, a preparation method thereof and an application thereof, wherein the amino acid type surfactant is formed by reacting an amino acid compound with a C ₂ -C ₇ fatty acid compound to have The amphoteric structure enhances the dispersion and compatibility between polarity and non-polarity. The amino acid type surfactant of the invention has good low toxicity, dispersibility and biocompatibility, and can be widely applied to cosmetic formula materials, such as emulsion, essence, lotion, cleansing oil and the like. In addition, the amino acid type surfactant of the invention has good biodegradability, does not cause pollution and damage to the environment, and can be widely used in industrial applications, such as dyeing and finishing auxiliaries, detergents, etc. It has industrial utilization.

Amino acids are mostly used in organic synthesis, petrochemical, medical and other fields in research. Because its structure is the basic substance composed of the human body, it is a necessity for human growth, development and nutrition. The main application in biology is to help the pituitary gland to function normally, stimulate growth hormone and remove toxins from the body, and maintain DNA integrity. Amino acids are far superior to traditional chemicals in their mildness to the human body and their low environmental pollution. Therefore, based on the premise that human beings pay attention to green environmental protection, further research on amino acids and their derivatives is of great significance.

Amino acids are the basic units that make up a protein, which imparts a specific molecular structure to the protein, making the molecule biochemically active. Protein is an important active molecule in the body, including enzymes and enzymes that catalyze metabolism. An organic compound having an amine group (-NH ₂ ) and a carboxyl group (-COOH) in an amino acid molecular structure, and both an amine group and a carboxyl group are directly bonded to a -CH- structure. The formula is H ₂ NCHRCOOH. The amino acid (C...CCCC-COOH) of α, β, γ, δ, ... can be classified according to the position at which an amine group is bonded to a carbon atom in a carboxylic acid. After hydrolysis of the protein, more than 20 alpha-amino acids are formed. Depending on the binding group, it may be classified into an aliphatic amino acid, an aromatic amino acid, a heterocyclic amino acid, a sulfur-containing amino acid, an iodine-containing acid or the like.

The basis of the amino acid as a surfactant can be traced back to 1909, and the hydrophobic group was first applied by glycine and alanine. Since then, amino acid type surfactants have had many research topics, and have great potential for application in the human market, such as medicine, cosmetics, food, and the like. The surfactant of the amino acid type is classified into an acidic amino acid, a basic amino acid or a neutral amino acid. Amino acid-based surfactants are synthesized as a starting material for the hydrolysis of proline, glycine, alanine, arginine, aspartic acid, leucine, serine, proline and protein. It is used in commercial and experimental research.

At present, amino acid surfactants are used in various fields under the heading of a green environment. In the achievements of cosmetics, it has been confirmed that the amino acid esters and sulfhydryl groups have excellent emulsifying properties and strong antibacterial properties, and are biodegradable surfactants which exhibit low toxicity and exhibit antibacterial activity. It is an important property of amino acids and their derivatives. Amino acid surfactants are relatively high-temperature anionic surfactants, but globally in the traditional anionic interface activity The use of the agent, due to the environmental burden and high allergic irritancy, has been gradually replaced by non-ionic surfactants since 2001. However, the amino acid-based anionic surfactants have a growth rate of 21% in 2003 due to their low environmental burden and low allergic irritancy, coupled with the better decontamination effect of anionic surfactants. Traditional anionic surfactants have been unable to stand. From this, it can be seen that the market for surfactants will be an amino acid type surfactant having environmentally friendly, low irritation, hypoallergenic irritant and potent decontamination effects.

Nowadays, amino acid surfactants are mostly obtained by reacting an amino acid with a long-chain fatty acid, and are usually formed by reacting with a fatty acid having 8 to 22 carbon atoms to have a structure having a hydrophilic-hydrophobic group. The present inventors have carefully studied that amino acid can also form an amino acid surfactant by reacting with a short-chain fatty acid, and unexpectedly found that these surfactants have an interface obtained by reacting an amino acid with a long-chain fatty acid in the prior art. The active agent has more excellent surfactant properties.

The invention relates to a method for preparing an amino acid type surfactant and an application thereof, which are prepared by using an amino acid compound and a C ₂ -C ₇ fatty acid compound to have good biodegradability and no environmental pollution. The active agent, because of its special chemical structure, is easily adsorbed on the surface or interface of the solution at a very low concentration, thereby changing the free energy of the surface or interface of the solution to reduce the surface tension, resulting in wetting, penetration, foaming, and emulsification. Characteristics such as dispersion and melting.

The amino acid type surfactant of the present invention is formed by reacting an amino acid compound with a C ₂ -C ₇ fatty acid compound, wherein the amino acid compound is selected from the group consisting of a material containing an amine group and a carboxylic acid, Glycine, Alanine, Valine, Leucine, Isoleucine, Phenylalanine, Tryptophan, tyrosine (Tyrosine), Aspartic acid, Histidine, Asparagine, Glutamic acid, Lysine, Glutamine At least one or more of Methionine, Arginine, Serine, Threonine, Cysteine, Proline . It is mainly used for sarcosine, valine, aspartic acid, serine, alanine, valine, leucine, arginine, etc., of which the former two are particularly commonly used.

In particular, proline is preferred. In the present embodiment, glutamine is used as an important excitatory neurotransmitter in the central nervous system of animals. There are three major types of specific receptors: AMPA (α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid), NMDA (N-methyl-D-aspartic acid) and Caying Acid (Kainate, red alginate/hainic acid). In addition, glutamate is mainly used for the treatment of hepatic coma in medicine, and is also used to improve children's mental development. In the food industry, glutamic acid (MSG) is a commonly used food preservative, and its main component is glutamine. Sodium salt.

The amino acid type surfactant of the present invention, wherein the C ₂ -C ₇ fatty acid compound may be a linear or branched fatty acid, and may be a fatty acid of a monocarboxylic acid, a dicarboxylic acid or a polycarboxylic acid, and may be Hydroxy-substituted fatty acid selected from the group consisting of acetic acid, propionic acid, hydroxypropionic acid, isopropyl acid, malonic acid, butyric acid, hydroxybutyric acid, succinic acid, isobutyric acid, valeric acid, valproic acid, 3-methyl Butyric acid, ethyl propionic acid, glutaric acid, glutamic acid, isovaleric acid, hexanoic acid, hydroxycaproic acid, isohexanoic acid, adipic acid, isohexanoic acid, heptanoic acid, hydroxyheptanoic acid, pimelic acid, etc. At least one or more.

The amino acid type surfactant of the present invention preferably comprises an amine group formed by linking a natural α-amino acid with a C ₂ -C ₇ fatty acid through an α-amino group, an α-COOH or a branched group. Acid type surfactant.

The amino acid type surfactant of the invention has excellent properties, and has excellent performances such as surface tension, foaming property, foam stability, emulsifying property or dispersibility, and has good low toxicity. Dispersibility and biocompatibility, it can be used as a good surfactant for green and environmental protection. It can be widely used in cosmetic formulas such as lotions, essences, lotions, cleansing oils, etc. In addition, the amino acid type surfactant of the invention has good biodegradability, does not cause pollution and damage to the environment, and can be widely used in industrial applications, such as dyeing and finishing auxiliaries, detergents, etc. It has industrial utilization.

The invention relates to a method for preparing an amino acid type surfactant, and the preparation method can be divided into a direct method and an indirect method according to the starting reaction raw materials.

The direct method refers to the preparation of a condensation reaction of a fatty acid or a fatty acid ester (animal and vegetable oil) with an amino acid. Since the condensation reaction of the direct method requires high chemoselectivity, the reaction conditions of the method are not easy to control, and the reaction yield is not high, and a special catalyst is generally required. The N-mercapto-amino acid type surfactant is a green chemical product, but if the preparation time is too long in the production process, the product will be gradually eliminated by the society if the industrial "three wastes" are excessive. In recent years, with the concept of “green chemistry”, it is increasingly required that chemical products be produced from the source with a green concept. The direct method is easy to prepare raw materials, simple in preparation method, and conforms to the concept of “green chemistry”. The research work on synthesizing N-mercapto-amino acid type surfactants by this method is increasing. Enzymatic synthesis is the main direction of direct law research. The enzyme synthesis method of N-mercapto-amino acid type surfactant was first proposed by Nordisk et al. The rapid development of enzyme-catalyzed reaction in non-aqueous medium provides a new development opportunity for such bio-organic synthesis. Enzyme preparations commonly used in enzyme-catalyzed synthesis mainly include proteolytic enzymes and lipases, both of which are relatively easy to obtain. The reaction system is mostly used Machine solvent system, commonly used organic solvents are n-hexane, acetonitrile, ethyl acetate, toluene and isooctane.

The indirect synthesis preparation includes the preparation of a deuteration reaction of a fatty acid anhydride with an amino acid salt, the preparation of a fatty acid hydrolysis reaction, the preparation of a hydroxylamine hydroxylation reaction, and the reaction of a fatty acid chloride with an amino acid (Shawton-Baumann method). Recently, there have also been related studies on the preparation of stearic acid by esterification with a coupling agent followed by condensation with an amino acid. At present, N-mercaptoamino acid and its salt are mainly prepared by Schotten-Banmann condensation reaction in the industry, which is composed of aliphatic hydrazine and amino acid in alkaline aqueous solution or other organic solvent. The N-decylamino acid salt is obtained by a one-step process, and then the N-decylamino acid preliminary product is obtained by neutralization with a mineral acid, and then neutralized to form a N-mercaptoamine acid salt having a higher purity. The advantages of this method are simple operation, mild reaction conditions, low reaction temperature, high yield, and easy application in practical industrial production. Taking Creatine as an example, the specific synthesis step (RCOOH is a fatty acid) is prepared by the Shorton-Baumann method:

The synthesis of the amino acid type surfactant of the present invention can be carried out by the above direct or indirect preparation process. In the embodiment of the present invention, the direct method is used, and the selected amino acid is first reacted with the fatty acid to make it into a structure. At the same time, the hydrophilic end and the hydrophobic end constitute an amphipathic structure. The synthesis temperature is 0-220 ° C, and the synthesis time is about 1 to 10 hours. The catalyst is titanium isopropoxide, sulfuric acid, hydrochloric acid or a group thereof, wherein amino acid: fatty acid The amount of addition is 0.1:10~10:0.1 molar ratio.

Figure 1. Foaming test chart of amino acid type surfactant product

Preparation of amino acid type surfactant

Use materials:

(1) Glutamic acid

(2) Arginine

(3) Acetic Acid C ₂

(4) Butyric Acid C ₄

(5) 3-Methylbutanoic acid C ₆

(6) Octanoic acid C ₈

(7) Lauric Acid C ₁₂

(8) Myristic Acid C ₁₄

The synthesis of the amino acid type surfactant is as follows:

(1) The glutamic acid or arginine and the catalyst were placed in a four-necked reaction flask equipped with a Teflon stir bar and a temperature control rod, and the temperature was raised to 180 ° C for 6 hr to obtain the first stage product.

(2) A series of fatty acids and a first-stage product were added to the bottle, and the catalyst was heated to 180 ° C for 6 hr.

(3) The synthesized product was dissolved in 95% ethanol (2:1), and salts and impurities were precipitated and filtered. The obtained product solution was subjected to a reduced pressure concentrating apparatus to remove the residual solvent, and placed in a vacuum oven to completely remove the solvent.

Determination of the properties of amino acid type surfactants

Surface tension measurement

CBVP-A3, Kyowa Kaimenagaku Co. LTD., Japan., was tested using a digital pendant white gold sheet surface tension meter.

(1) First complete the calibration procedures for the instrument.

(2) Wash the platinum tablets with alcohol and pure water, then burn the platinum tablets to the fire red with alcohol lamp to cool and then hang on the hook.

(3) After washing and drying the glass culture dish, about 10 ml of the test solution is injected, and placed on a lifting platform.

(4) Start the instrument switch to make the lifting platform rise slowly. When the liquid level of the liquid to be tested touches the platinum piece, the lifting platform will automatically stop and record the surface tension value when it is stable.

(5) Repeat the above steps 3 times and find the average value.

Contact angle measurement

FTA, FTA-125, tested with a photographic contact angle meter.

(1) Adjust the focal length and brightness contrast of the lens to complete the calibration procedures.

(2) Prepare sample solutions of different concentrations.

(3) Select the test board to be wetted (PVC, Acrylic)

(4) Drop the sample solution on the test board, and draw the screen to display the contact angle after computer calculation (Contact Angle) value.

(5) Repeat the procedure 3 times to measure the average value.

Foaming determination

Model KD-10, Daiei Kagaku Seiki MFG. Co. LTD., Japan, determined by the Ross and Miles method.

(1) Prepare 500 ml of a 1 wt% sample solution and place it in the sample tank.

(2) The fixed motor flow rate is 400ml/min. After the aqueous solution is pressed out by the circulating pump, it is continuously injected into the receiving tray through the nozzle. When the liquid reaches the certain height, the liquid will automatically overflow and maintain the liquid level to a certain height.

(3) The overflowed sample solution is automatically recycled back to the test tank for recycling. After 1 hour of circulation, the foam height in the measuring cylinder is recorded, which is the maximum foam height of the sample.

(4) Turn off the pump and record the foam height after 5 minutes. This is the foam stability.

Emulsifying ability

(1) Formulating a 1 wt% auxiliary solution.

(2) Weigh 10% by weight (O/W) of the olive oil auxiliary solution and 10% by weight (O/W) of the squalane auxiliary solution.

(3) Stirring was carried out for 10 min at a rotational speed of 11,000 rpm with a homogenizer (Ultra Turrax T25 Homogenizer) and allowed to stand for 10 min.

(4) The interface potential of each emulsion was measured by an interface potentiometer (Colloidal Dynamics, Zeta Probe Analyzer).

(5) The particle size and distribution of each emulsion droplet were measured by a Particle Size Distribution Analyzer.

Comparison of Examples 1 to 6 of the present invention with Comparative Examples 1 to 4 shows an amino acid type surfactant obtained from an amino acid and a short chain fatty acid C ₂ to C ₆ , which is composed of an amino acid and a long chain. The amino acid type surfactant obtained from the fatty acid C ₈ ~ C ₁₄ has more excellent properties, and has excellent performance in surface tension, foaming property, foam stability, emulsifying property or dispersibility, and can be used as A good surfactant for green and environmental protection.

The features, aspects, advantages and advantages of the invention are set forth in the description of the embodiments of the present invention, and the descriptions of the embodiments used herein are merely for the purpose of illustration and description. The scope of patents in the actual implementation of the present invention should be limited to the proportions listed in the attached table.

Claims (11)

A method for preparing an amino acid type surfactant, which is formed by directly reacting an amino acid compound with a C ₂ -C ₇ fatty acid compound, which is carried out by a condensation (dehydration) reaction method, wherein the amino acid is used The compound is selected from materials having an amine group and a carboxylic acid in the structure, and wherein the fatty acid compound is selected from a linear or branched chain fatty acid. A method of producing an amino acid type surfactant according to the first aspect of the invention, wherein the amino acid compound is selected from the group consisting of natural amino acids. The method for preparing an amino acid type surfactant according to claim 1, wherein the amino acid compound is selected from the group consisting of Glycine, Alanine, Valine, and Whiteamine. Acid (Leucine), Isoleucine, Phenylalanine, Tryptophan, Tyrosine, Aspartic acid, Histidine, Tianmen Asparagine, Glutamic acid, Lysine, Glutamine, Methionine, Arginine, Serine And at least one or more of threonine, Cysteine, and Proline. A method for producing an amino acid type surfactant according to the first aspect of the invention, wherein the fatty acid compound is selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, or a fatty acid of a polycarboxylic acid. The method for preparing an amino acid type surfactant according to claim 1, wherein the fatty acid compound is selected from the group consisting of acetic acid, propionic acid, hydroxypropionic acid, isopropyl acid, malonic acid, butyric acid, hydroxybutyric acid, Succinic acid, isobutyric acid, valeric acid, hydroxyvaleric acid, 3-methylbutyric acid, ethylpropionic acid, glutaric acid, glutarate, isovaleric acid, caproic acid, hydroxycaproic acid, isohexanoic acid, Adipic acid, isohexanoic acid, At least one or more of heptanoic acid, hydroxyheptanoic acid, pimelic acid, and the like. The method for preparing an amino acid type surfactant according to the first aspect of the patent application, wherein the synthesis temperature is 0 to 220 ° C, the synthesis time is 1 to 10 hours, and the catalyst is titanium isopropoxide or sulfuric acid. Any one of or a group of hydrochloric acid, wherein the amino acid: fatty acid is added in an amount of from 0.1:10 to 10:0.1. An amino acid type surfactant prepared by the method for preparing an amino acid type surfactant according to any one of claims 1 to 6. A dispersant material which is an amino acid type surfactant prepared by a method for preparing an amino acid type surfactant as disclosed in any one of claims 1 to 6, or as claimed in the patent application. The amino acid type surfactant of the seventh item is the main constituent material. For example, the dispersant material of claim 8 is used as a fiber dyeing and finishing aid, an inorganic nano-powder dispersant, and the like in a related application field. An emulsifier material which is an amino acid type surfactant prepared by a method for preparing an amino acid type surfactant as disclosed in any one of claims 1 to 6, or as claimed in the patent application. The amino acid type surfactant of the seventh item is the main constituent material. For example, the emulsifier material of the patent application scope 10 is used as a cosmetic emulsifier, a food emulsifier, and the like, and related application fields related to emulsification.