TWI802910B - Preparation method and its application of caffeic acid-amino acyl type surfactant - Google Patents

Abstract

The caffeic acid-amino acyl type surfactant of the present invention uses polyethylene glycol, amino acyl salt, and dihydrocaffeic acid as main raw materials. The synthesis of the surfactant includes step (a) acidification of amide acid salt; Step (b) synthesis of caffeic acid-amino acyl type surfactants, dihydrocaffeic acid and amino acyl compounds are linked by polyethylene glycol with different EO chain lengths to synthesize a series of caffeic acid -amino acyl type surfactant.

The caffeic acid-amino acyl surfactant of the present invention is natural and environmentally friendly and non-toxic. It can be used as a dispersant for inorganic nanopowder dispersants, fiber dyeing and finishing auxiliary, and as an emulsifier for cosmetics and pharmaceuticals, food, industrial products and other emulsification fields.

Description

Preparation and Application of Caffeyl Amino Acid Type Surfactant

The caffeic acid amide acid type surfactant of the present invention, take polyethylene glycol, amide acid salt, dihydrocaffeic acid as main raw material, synthesis comprises step (a) acidification of amide acid hydrochloride, is the amide Amino acid salt is acidified into amido diacid compound with inorganic acid; and the synthesis of step (b) caffeic acid amido acid type surfactant is to dihydrocaffeic acid and amido diacid compound by different Polyethylene glycol chains with EO chain lengths are used to synthesize a series of caffeic acid-based surfactants. The caffeic acid amide acid-type surfactant of the present invention is natural, environmentally friendly and non-toxic, and can be used as a dispersant for inorganic nano-powder dispersants, fiber dyeing and finishing auxiliaries, and as an emulsifier for cosmetics and pharmaceuticals , food, industrial products, etc. in the field of emulsification.

In recent years, due to the rapid development of industry, there have been two serious problems affecting human existence, one is the energy crisis and the other is environmental pollution. Environmental protection and safety are the main driving forces for the future development of the surfactant industry. It is of great significance to evaluate the environmental safety of the possible hazards of surfactant pollution, degradation performance and accumulation performance in the environment. In the prior art, it is generally believed that cationic surfactants are more toxic and are often used for sterilization; anionic surfactants have certain toxicity; nonionic surfactants are relatively less toxic, but some degradation products are very toxic , often have to be discarded after use, which is likely to cause environmental pollution. Therefore, when using surfactants, in addition to considering their interface activity and functionality, whether they will cause environmental pollution Evaluation is very important.

Petroleum is the raw material of traditional surfactants, which are called petrochemical surfactants. They have poor decomposition and may even be toxic. They not only pose a threat to the environment, but also may cause human skin protein denaturation, skin aging and dryness, and damage the barrier function of the skin. The ingredients take the opportunity to penetrate into the skin and enter the human body through breathing or through the mouth or skin, causing continuous and cumulative chronic damage. In addition, there is a type of petrochemical surfactant containing nonylphenol, which is an "environmental hormone". When it flows into water, it pollutes rivers and oceans, and also causes pollution problems such as river pollution, destroying the balance of the natural ecological environment.

Decomposable surfactants are also known as temporary surfactants or surfactants with controlled half-life (surfactants with controlled half-live). A class of surfactants that can be decomposed into non-surface active substances or transformed into new surface active compounds under the action of heat or light. Such surfactant molecules often contain a weak bond with limited stability between the polar end and the hydrophobic chain. The cleavage of the weak bond will directly destroy the interfacial activity of the molecule, which is commonly referred to as the primary decomposition of the surfactant. According to the different decomposable functional groups, decomposable surfactants can generally be divided into two categories: acetal type and ketal type. Compared with general surfactants, decomposable surfactants have a better concept of environmental protection, and this kind of surfactants can eliminate some complicated situations. In recent years, people's understanding of decomposable surfactants has been continuously deepened and developed. The size of the impact on the environment and the speed of biodegradability have gradually become a very important indicator for judging the quality of surfactants.

The function of surfactant:

(1) Cleaning effect Surfactants can coat oil or dirt and take it away with the solution to achieve cleaning effect. Such as soap, shampoo, facial cleanser, shower gel, toothpaste, etc. They all use surfactants with a cleaning effect as their main raw materials. Among them, anionic surfactants are used as the main agent, while non-ionic, zwitterionic and cationic surfactants are appropriately added as auxiliary agents depending on the characteristics of the product.

(2) Foaming effect Some surfactants are easy to wrap air into a stable film, and have foaming as a surfactant for discussion and application. Cleaning supplies such as shampoo, toothpaste, and shower gel.

(3) Emulsification The surfactant can make the oil phase into small particles and disperse in the water phase to achieve emulsification. For example, fruit acid products with extremely high acidity, plant essential oil products with high volatility, and physical sunscreen (titanium dioxide, zinc oxide) products with high specific gravity.

(4) Melting effect Some non-ionic surfactants can dissolve oil-soluble components in water, but there are not many surfactants with this melting effect, mainly ether (ETHERS) surfactants. The difference between melting and emulsification is that melting is usually in the form of a transparent liquid or gel, while emulsification is in the form of a milky opaque liquid or cream. Solubilization is that the surfactant disperses the oil in the aqueous solution with very fine droplets. Transparent because light can pass through. Emulsification, the dispersed droplets of the oil have larger particles, which can refract or reflect light, so they are white.

(6) The wetting effect can reduce the surface tension by the surfactant, so that the substances that are not easy to adsorb and adhere are easy to adsorb and adhere. For example, an oily surface is permeable to a water-based substance, or a water-based surface is permeable to an oily substance. The greatest achievement in the study of interface chemistry is the invention and application of surfactants. The most important characteristic of surfactants is that they can reduce the surface and interfacial tension, and produce wetting, penetration, emulsification, dispersion and other functions. Therefore, it can be widely applied to various industries. Especially in the textile industry and cosmetics manufacturing, all kinds of cosmetics containing oil and water need to be bound There are suitable surfactants to emulsify oil and water into a stable homogeneous substance, so it is also an indispensable raw material in the cosmetics production process.

Under the trend of global stable development, surfactants provide an excellent environment for the development of related industries, and the requirements for product structure, items, performance and technology are getting higher and higher. Therefore, the development of safe, mild, natural, biodegradable and special surfactants provides a good foundation for the development and application of new products.

Caffeic acid, also known as 3,4-dihydroxycinnamic acid, is an organic compound belonging to hydroxycinnamic acid, which has two functional groups of phenolic hydroxyl and acrylic acid. Because caffeic acid is a key intermediate in the biosynthesis of lignin, one of the main components of plant biomass and its residues, it is widely present in various plants. It is soluble in hot water and ethanol, slightly soluble in cold water. It is yellow-white crystal at room temperature. Caffeic acid is the most widely distributed hydroxycinnamate and phenylpropane metabolite, and can therefore be found in many places, found in goldenrod (Asteraceae), Sanlihong (Rosaceae), Willow (Sapinaceae), Cimicifuga ( Ranunculaceae), Eurasian water keel (Tythyaceae), lemon (Rutaceae), succulents (Polygonaceae), valerian (Lonicaceae), thyme (Lamiaceae), Eucommia (Eulmoides) and other Chinese herbal plants. It has the functions of shrinking and strengthening microvessels, promoting the function of coagulation factors, and increasing white blood cells and platelets. It is used for various pharmacological effects such as the treatment of white blood cells and thrombocytopenia, anti-oxidation, anti-tumor, and brain protection.

Caffeic acid can effectively inhibit the lipid peroxidation of linoleic acid emulsion, and is more effective than α-tocopherol (α-tocopherol), butylhydroxyanisole (BHA), dibutylhydroxytoluene (BHT) and water-soluble vitamin E ( trolox) stronger reduction. The photoprotective effect of caffeic acid is due to its own antioxidant activity. Normal human lymphocytes are very sensitive to ultraviolet radiation. Lymphocytes exposed to ultraviolet light will experience lipid peroxidation, DNA damage and reduced cell viability, and will undergo radical oxidation reactions and die. Pretreatment of lymphocytes with caffeic acid can significantly reduce the lipid overload caused by ultraviolet radiation Oxidation, elevated levels of thiobarbituric acid reactants and conjugated dienes, DNA damage, and cell death. Caffeic acid can inhibit the growth, differentiation and proliferation of a variety of tumor cells, and promote tumor cell apoptosis, reduce the adverse reactions of anticancer drugs, and prevent the transformation of chemical cancer treatment. Studies have found that caffeic acid can play an anti-cancer role by affecting the microRNA regulatory network. On the other hand, caffeic acid can induce tumor cell apoptosis by regulating the level of reactive oxygen species in glandular mitochondria in tumor cells. In terms of anti-tumor, caffeic acid not only has a great effect by itself, but also has a synergistic effect with other drugs.

Lipstick has always been loved by women who love beauty. It is a cosmetic commonly used by women. However, due to the difference in quality and formula and the difference in consumer physique, there are various dangers hidden when using lipstick. At the same time, it is inevitable to inadvertently bring lipstick into the body. The preservatives and antioxidants BHA in lipsticks have been proven to be quasi-carcinogens, and preservatives can cause breast tumors.

The world consumes a large amount of specialty chemicals-surfactants every day, so many studies have been conducted on biodegradable surfactants, in order to allow consumers to use less irritating, less toxic and green environmental protection Therefore, the novel caffeic acid amino acid surfactant of the present invention is most in line with the concept of modern green environmental protection.

The caffeic acid-based surfactant of the present invention is a renewable raw material that can be decomposed by nature, so it will not cause environmental burdens. In addition, caffeic acid has a huge antioxidant potential, and it has been proved to have antibacterial properties in vitro Amino acid compounds have skin-friendly, moisturizing and anti-aging effects, so they are considered as the best formula to replace traditional surfactants in the fields of pharmaceuticals, food, specialty chemicals and cosmetics.

The caffeic acid amino acid type surfactant of the present invention is a polymer with good dispersibility Ethylene glycol, dihydrocaffeic acid and amide acid salt are the main raw materials, and polyethylene glycol (different EO chain lengths: PEG200, PEG400, PEG600, PEG1000) is used as the hydrophilic group segment. The synthesis includes step (a) amide Acidification of amino acid hydrochloride is to acidify amido acid salt with inorganic acid into amidodiacid compound; and step (b) synthesis of caffeic acid amido acid type surfactant is to combine dihydrocaffeic acid and A series of caffeic acid-based surfactants are synthesized by linking diacid compounds with polyethylene glycols of different EO chain lengths.

The caffeic acid amino acid type surfactant of the present invention is used as a dispersant, applied to fiber dyeing and finishing auxiliary agent, dispersant of inorganic nanopowder, and used as emulsifier, applied to cosmetics, pharmaceuticals, food, industrial products In the field of emulsification.

Caffeic acid amino acid type surfactant of the present invention is the surfactant with general formula (I) structure,

n: the number of repeating units of polyethylene glycol, the value is 2-10000, preferably 5-5000.

y: repeating number of the -CH ₂ - segment next to the longer-chain acid group in the amidodiacid compound, the value is an integer number of 1-30, preferably 1-20.

R: A long-chain saturated or unsaturated hydrocarbon organic group with a carbon chain number of 6-30.

The preparation method of the caffeic acid amido acid type surfactant of the present invention uses polyethylene glycol with good dispersibility, dihydrocaffeic acid and amido acid salt as main raw materials, and the synthesis includes step (a) amido Acidification of hydrochloric acid; and step (b) synthesis of caffeic acid-type surfactant. Among them, poly Ethylene glycol (different EO chains: PEG200, PEG400, PEG600, PEG1000) is used as the hydrophilic group segment, wherein the amide amino acid is preferably a diacid compound, which has the chemical structure of the following general formula (II):

y: repeating number of the -CH ₂ - segment next to the longer-chain acid group in the amide acid diacid compound, the value is an integer number of 1-30, preferably 1-20.

R: A long-chain saturated or unsaturated hydrocarbon organic group with a carbon chain number of 6-30.

The preparation method of the caffeic acid amino acid type surfactant of the present invention, comprises (a) to (b) synthetic steps are as follows:

(a) acidification of amide acid hydrochloride

Acidifying the amido acid salt with a mineral acid into an amidodiacid compound;

(b) Synthesis of caffeic acid-type surfactant

The dihydrocaffeic acid and amidodiacid compounds are linked by polyethylene glycols of different chain lengths (different EO chains: PEG200, PEG400, PEG600, PEG1000) to synthesize a series of caffeic acid amido acid types Surfactant.

The preparation method of the caffeamide acid-type surfactant of the present invention, the step (a) acidifies the amido acid salt with an inorganic acid into an amidodiacid compound, wherein the concentration of the inorganic acid is 0.1-3M.

The preparation method of the caffeic acid amido acid type surfactant of the present invention, wherein, step (b) is to place the polyethylene glycol of different chain length, dihydrocaffeic acid, and amido diacid compound in reaction bottle , add a catalyst, and react at a temperature of 80-180°C for 4-10 hours to obtain a series of polymers Ethylene glycol-modified caffeic acid-type surfactant product.

The preparation method of the caffeic acid amino acid type surfactant of the present invention, wherein, the catalyst of step (b) is selected from: 4-dimethylaminopyridine (DMAP), titanium isopropoxide (titanium isopropoxide), sulfuric acid ( Sulfuric acid), hydrochloric acid (Hydrochloric acid) at least one.

The synthesis reaction formula of the caffeic acid amino acid type surfactant of the present invention is as follows: Wherein the amido acid salt compound is example with sodium lauryl glutamate, polyethylene glycol (change different EO chains: PEG200, PEG400, PEG600, PEG1000) as the hydrophilic segment.

step (a)

step (b)

The present invention synthesizes a series of caffeic acid amino acid type surfactants. The code names are PEG200, PEG400, PEG600, PEG1000.

The caffeic acid-based surfactant of the present invention is used as a dispersant material, and can be used as a fiber dyeing and finishing auxiliary agent, a dispersant for inorganic nanopowder, and the like.

The caffeic acid-based surfactant of the present invention is used as an emulsifier material, and can be used in the field of emulsification of cosmetics, pharmaceuticals, food, industrial products, etc.

The basic property measurement of the caffeic acid amino acid type surfactant of the present invention:

1. Surface tension measurement

Molecules in any substance have the force of mutual attraction, and the molecules on the liquid surface will be affected by different gravitational forces on the liquid surface. But the gravitational force on the air is almost zero, and the gravitational force that pulls down on the inside of the liquid is surface tension. As the concentration of the surfactant increases, the surface tension value decreases. When the concentration increases to a certain extent, the surfactant molecules in the solution begin to attract each other with hydrophobic groups and form microcells. The concentration when the microcells begin to form , which is called the critical micelle concentration (Critical Micelle Concentration; CMC), and this tight arrangement mode will reduce the gravitational force that the molecules on the surface of the solution are pulled to the inside, reduce the free energy of the liquid surface, and reduce the surface tension. Adding a surfactant will reduce the surface tension. The reason is that the hydrophobic end of the surfactant forms a hydrophobic film on the water surface; while the hydrophilic end faces the interior of the liquid. This arrangement reduces the free energy of the solution surface.

Use a digital hanging platinum sheet (type) surface tension tester to test

Brand Model: CBVP-A3, Kyowa Kaimenagaku Co.LTD., Japan.

(1) Complete the calibration procedures of the instrument first.

(2) Wash the platinum piece with alcohol and pure water, then burn the platinum piece with an alcohol lamp until it is fiery red, let it cool down and hang it on the hook.

(3) Wash and dry the glass petri dish, inject about 10ml of the solution to be tested, and place it on the lifting platform.

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

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

The surface tension test of caffeic acid-based surfactants, the test results are shown in Figure 1.

2. Contact angle measurement

Under normal circumstances, the surface of an object will be covered with a layer of air. In order for the liquid to extend and expand on the solid surface, the covered air must be removed first. This phenomenon of replacing the original air with liquid is called wetting. Surfactants have the ability to reduce the surface tension and free energy of a liquid, and can exhibit its wettability. The contact angle is also an instrument for judging the wettability of a specific liquid to a solid surface. The tangent line extending from the edge of the water droplet at the intersection point of contact between the water droplet and the solid body, the angle formed by the tangent line and the solid surface is the contact angle (θ). The smaller the contact angle, the better the wetting effect of the sample on the solid surface, and the surfactant has the ability to reduce the surface tension and free energy of the liquid, so it has wettability.

Use a contact angle meter, FACE CA-5 contact angle meter, place a standard plate on the material table to be tested, draw the sample solution with the injection syringe, and control the size of the droplet to about 20mm.

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

(2) Using pure water as the standard, prepare sample solutions with different concentrations.

(3) Drop the sample solution on a glass plate or a Teflon plate, and display the contact angle value after computer calculation.

(4) Repeat the step 3 times to measure the average value.

The concentration of caffeic acid amino acid type surfactant is 1wt%, 0.1wt%, 0.01wt% in glass Figure 2 and Figure 3 show the contact angle diagrams on glass and Teflon plates.

3. Foaming

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

(1) Prepare 500.0mL of 0.5wt% sample solution and place it in the sample tank.

(2) The flow rate of the fixed motor is 400.0mL/min. After the aqueous solution is pressed out by the circulating pump, it flows out through the nozzle and is continuously injected into the receiving plate. When the solution in the receiving plate reaches a certain height, it will automatically overflow to keep the liquid level at a certain height. .

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

(4) Turn off the pump, and record the foam height after 5 minutes, which is the foam stability. The results of the foaming properties of the caffeic acid-type surfactant of the present invention are shown in FIG. 4 .

4. Conductivity

The conductivity of water is an indicator of the comprehensive conductivity of all ions in water by borrowing the concept of electrochemistry. The higher the conductivity, the more substances that contain corrosion and scale formation factors. The lower the conductivity, the less ions or conductive substances contained in the water, so the conductivity can be used in water quality management indicators. When the electrolyte is dissolved in water, it will dissociate into cations and anions. When the current is about to pass through the solution, electrons can flow between the positive and negative electrodes through the movement of the anions and cations, and the solution can conduct electricity. The conductivity is mostly used to measure the critical cell concentration (CMC) of the ionic surfactant solution. Generally speaking, the conductivity of the solution should be proportional to the solute concentration. The surfactant of the present invention can not only investigate its critical cell concentration (CMC), but also analyze the change of its hydrophobic chain with respect to the electrical conductivity. Carry out conductivity by caffeic acid amide acid type surfactant concentration 1wt%, 0.1wt%, 0.01wt% The test results are shown in Figure 5.

5. COD (Chemical Oxygen Demand)

Chemical Oxygen Demand (COD) refers to the amount of oxygen consumed by organic substances in water under acidic and high-temperature conditions, which are oxidized to CO ₂ and H ₂ O by chemical methods through strong oxidants. The size of the COD value can indicate the amount of organic matter in the water. Under certain conditions, the amount of oxidant consumed to oxidize the reducing substances in 1 liter of water sample is used as an indicator, and the required milligrams of oxygen are converted into per liter. After the water sample is completely oxidized, it is expressed in mg/L to reflect the degree of pollution by reducing substances in the water, and this index is also used as one of the comprehensive indicators of the relative content of organic matter.

According to the difference of detection environment and impurities in water samples, the main detection methods in the world are potassium dichromate method and potassium permanganate method. The analysis method adopted by this type of COD analyzer is potassium dichromate method, and the data accuracy of this method is high. , less disturbed by the natural environment, as the preferred method for the determination of COD indicators. Chemical principle: Mix the water sample to be tested, potassium dichromate, silver sulfate, and concentrated sulfuric acid in a certain proportion and gradually heat to 175°C for digestion. During this period, chromium ions are converted from VI to III as oxidants. The color is changed, and the degree of color change is in a positive correspondence with the content of organic compounds in the sample. Finally, the COD value of the water sample is directly displayed through colorimetric conversion. Chemical Oxygen Demand Spectrophotometer, HACH, Model DR/2800 Chemical Oxygen Demand Reactor, Rocker, Model CR25

(1) Prepare 2.00mL of sample solutions with different concentrations and place them in colorimetric tubes.

(2) Put the colorimetric tube into the COD heater and wait until the temperature rises to 120°C.

(3) After cooling to room temperature, read the value with COD chemical oxygen demand spectrophotometer. COD chemistry of a series of caffeic acid-type surfactants measured at concentrations of 1wt% and 0.1wt% Oxygen demand, as shown in Figure 6.

Figure 1 Surface tension diagram of caffeic acid-based surfactants

Figure 2 Contact angle diagrams of caffeic acid-based surfactants with concentrations of 0.5wt%, 0.1wt%, and 0.01wt% on glass plates

Figure 3 The contact angle diagrams of caffeic acid-based surfactants with concentrations of 0.5wt%, 0.1wt%, and 0.01wt% on Teflon plates

Figure 4 Foaming height diagram of caffeic acid-based surfactant (concentration 0.5wt%)

Figure 5 Contact angle images of caffeic acid-based surfactants (concentration 1wt%, 0.1wt%)

Figure 6. Conductivity diagram of caffeic acid-type surfactant concentration 1wt%, 0.1wt%, 0.01wt%

Figure 7 COD chemical oxygen demand test chart of caffeic acid-type surfactant concentration 1wt%, 0.1wt%

The preparation of caffeic acid amide type surfactant of the present invention

Comprising the following synthetic steps (a) to (b):

(a) acidification of amide acid hydrochloride

Add 30 moles of sodium lauryl glutamate (amyl acid salt) to 30 moles of 1M dilute hydrochloric acid to acidify sodium lauryl glutamate hydrochloride, put it in a hot air circulation oven for drying, and obtain product A.

(b) Synthesis of caffeic acid-type surfactant

Put 30 moles of polyethylene glycol (changes in different polyoxyethylene (EO) chains: PEG200, PEG400, PEG600, PEG1000), 30 moles of dihydrocaffeic acid and 30 moles of lauryl glutamic acid in a magnetic stirring and temperature control bar In the four-necked reaction flask, 4-dimethylaminopyridine (DMAP) was used as a catalyst and reacted at a temperature of 130° C. for 6 hours to obtain a series of polyethylene glycol-modified caffeic acid-type surfactant products B.

The caffeic acid amido acid type surfactant product of the present invention, take polyethylene glycol (change different EO chain: PEG200, PEG400, PEG600, PEG1000), dihydrocaffeic acid, amido acid salt as main raw material, synthesis Including step (a) acidification of amido acid salt, which is to acidify amido acid salt into amido diacid compound with inorganic acid; and step (b) synthesis of caffeic acid amido acid type surfactant, which is Dihydrocaffeic acid and amidodiacid compounds are linked by polyethylene glycol with different EO chain lengths to synthesize a series of caffeamide-type surfactants and obtain a series of caffeamide-type surfactants. Surfactant. The product codes are PEG200, PEG400, PEG600, PEG1000 respectively.

The surface tension of the caffeic acid amino acid type surfactant of the present invention

Adding a surfactant to an aqueous solution will reduce the surface tension. Because the structure of the surfactant itself contains hydrophilic groups and hydrophobic groups, the part of the hydrophilic group in the solution will stay in the water, while the part of the hydrophobic group will absorb and protrude from the water surface. lead to. Such an arrangement will reduce the asymmetric hydrogen bond force of water molecules on the surface, reduce the surface free energy, and thus cause the phenomenon of reduced surface tension. Assuming that the normal temperature is 25°C, the surface tension value is about 72.8mN/m, and the surface tension value decreases with the increase of the surfactant concentration. When the concentration increases to a certain extent, the surfactant molecules in the solution begin to attract each other with hydrophobic groups to form microcells, when the microcells start to form The concentration at this time is called the critical micelle concentration (Critical Micelle Concentration; CMC).

The surface tension figure of a series of caffeamide type surfactants of the present invention, as shown in Figure 1, can find from this figure, when a series of caffeamide type surfactant product concentration increases , the surface tension decreases, and when the decrease is 0.05wt%, it will not decrease. This concentration is called the critical cell concentration. The tension value is 28.8mN/m, the surface tension value of PEG1000 is 29.2mN/m, the order of surface tension is PEG400>PEG600>PEG1000>PEG200, and the range is 21.5~29.7mN/m. It can be known that PEG200 has the largest surface tension value, representing the worst interfacial activity, and PEG400 has the smallest surface tension value, representing the best interfacial activity, and can obtain the best effect when applied to detergents, cosmetics or drug coatings.

The contact angle of the caffeic acid amino acid type surfactant of the present invention

Take glass plate and Teflon plate as wet object, test the contact angle of a series of caffeic acid type surfactants of the present invention (product codes are respectively PEG200, PEG400, PEG600, PEG1000) product and test plate, wherein , the smallest contact angle between the product and the glass plate represents the best wettability of the product, and the largest contact angle between the product and the Teflon plate represents the worst wettability of the product. Figure 2 and Figure 3 are the contact angle diagrams of the caffeic acid-type surfactant product of the present invention, it can be seen from Figure 2 that PEG600 has the smallest contact angle at 1wt%, indicating the best wetting effect, and PEG1000 at 0.1wt% The highest % contact angle indicates poor wetting. Fig. 3 is the contact angle of a series of caffeic acid type surfactant products of the present invention on the teflon plate, as can be seen from Fig. 3, PEG1000 is the smallest at 1wt% contact angle, represents that wetting effect is the best, and PEG600 has a large contact angle at 0.1Wt%, indicating that the wetting effect is not good. Fig. 4 is the image figure of the contact angle of the caffeamide type surfactant product of the present invention, the contact angle of the caffeamide type surfactant product of the present invention The order of size is PEG200>PEG400>PEG600>PEG1000.

The foamability of the caffeic acid-based surfactant of the present invention is shown in Figure 5, and the foaming height of this series of caffeic acid-based surfactant concentration of 0.5wt% is about 0.5 to 2.5 cm, during the dyeing process, it is often necessary to add surfactants to improve the dyeing quality, but during the operation, the gas enters the dye solution due to the rotation of the machine, resulting in foam generation. Too much foam will hinder the contact between the dye liquor and the fiber, resulting in uneven dyeing. Therefore, the surfactant used in the dyeing and finishing process must have low foaming properties, and the foaming property is PEG600>PEG1000>PEG400>PEG200. Foam stability The density increases with the length of the PEG chain. The reason is that the longer the PEG is, the smaller the area occupied by the water film interface is, so it is easier to arrange closely and make it have better foam stability.

The electrical conductivity of the caffeic acid-type surfactant of the present invention. The present invention can not only investigate its critical cell concentration (CMC), but also analyze the change of its hydrophobic chain to electrical conductivity. A series of caffeic acid of the present invention Amino acid type surfactant product, the concentration is respectively 1wt%, 0.1wt%, 0.01wt% to carry out conductivity test, and its result is shown in Figure 6, know the conductivity of a series of surfactant products of the present invention The value ranges from 0 to 213μS/m, and the conductivity increases with the increase of the surfactant concentration. The conductivity is PEG200>PEG400>PEG600>PEG1000, and the conductivity decreases with the increase of the PEG chain length.

The COD chemical oxygen demand of the caffeic acid-based surfactant of the present invention is shown in Figure 7 as a COD figure of a series of caffeic acid-based surfactants, which are respectively 1wt% and 0.1wt%. Concentration detection, with the increase of the concentration of additives, the chemical oxygen demand increases significantly. When PEG1000 is at 0.1wt%, the COD value is the highest, indicating that more oxidants are needed to consume the COD value The size is PEG1000>PEG400>PEG200>PEG600, and PEG600 has the smallest COD value at 0.1wt%. In addition, comparing the chemical oxygen demand of the surfactant product of the present invention with that of the commercially available surfactant, it was found that the chemical oxygen demand of the surfactant of the present invention was lower than that of the commercially available surfactant, indicating that the caffeic acid amide of the present invention Amino acid-type surfactants are relatively green and environmentally friendly surfactants.

The surface tension measurement and analysis of a series of surfactant products synthesized by the present invention show that the surfactant products synthesized by the present invention all have the characteristics of reducing surface tension. /m.

The contact angle test of a series of surfactant products synthesized by the present invention shows that the contact angles of the synthesized surfactant products to glass plate (Glass), acrylic sheet (Acrylic Sheet) and Teflon plate (Telfon) are all Lower than pure water, showing its good wetting effect. The foamability test result of the caffeic acid amino acid type surfactant of the present invention shows that the foaming height of the synthesized surfactant is all below 5cm, so it has lower foamability, and can be used in cosmetic emulsions. No defoaming treatment is required, which can reduce costs.

Claims (10)

A kind of caffeic acid amino acid type surfactant, is the surfactant with general formula (I) structure,

In the formula, n represents the repeating number of polyethylene glycol, and its value is 2~10000; y represents the repeating number of the -CH ₂ - segment next to the longer chain acid group in the amido diacid compound, and its value is 1~30 Integer; R is a long-chain hydrocarbon organic group with 6-30 carbon chains. For example, a caffeic acid-based surfactant in item 1 of the scope of the patent application, wherein the polyethylene glycol repeat number n is 5-5000. For example, a caffeic acid amide acid-type surfactant as claimed in item 1 of the scope of the patent application, wherein the repeat number y of the -CH ₂ - segment next to the longer-chain acid group in the amide-based diacid compound is 1-20. A kind of preparation method of the caffeic acid amino acid type surfactant as any one in the 1st to 3rd of the scope of patent application, the synthesis step comprising (a) to (b) is as follows: (a) Acidification of amido acid salt is to acidify amido acid salt with inorganic acid into amidodiacid compound; (b) The synthesis of caffeic acid amino acid type surfactant is to synthesize caffeic acid amino acid type by linking dihydrocaffeic acid and amido diacid compounds through polyethylene glycol chains of different chain lengths Surfactant. For example, the preparation method of the caffeic acid-type surfactant of item 4 of the patent scope of the application includes the synthesis steps of (a) to (b) as follows: (a) acidification of amide acid hydrochloride Add amide acid salt to 0.1~3M dilute hydrochloric acid to acidify amide acid hydrochloride into amidodiacid compound; (b) Synthesis of caffeic acid-type surfactant Put polyethylene glycol, dihydrocaffeic acid, and amidodiacid compounds with different chain lengths in a reaction bottle, add a catalyst, and react at a temperature of 80-180°C for 4-10 hours to obtain a series of modified polyethylene glycols. Quality caffeic acid-type surfactant product. Such as the preparation method of the caffeamide amino acid type surfactant of item 5 of the scope of patent application, wherein, the catalyst of step (b) is selected from: 4-dimethylaminopyridine, titanium tetraisopropoxide, sulfuric acid, hydrochloric acid at least one. Such as the preparation method of the caffeic acid amino acid type surfactant of claim 6, wherein, the catalyst of step (b) is 4-dimethylaminopyridine. A dispersant material, which comprises the caffeic acid amide type surfactant as any one of items 1 to 3 in the scope of the patent application as a material, and it is used as a fiber dyeing and finishing auxiliary agent, inorganic nanopowder In the field of dispersants. An emulsifier material, which comprises the caffeic acid amide type surfactant as any one of items 1 to 3 in the scope of the patent application. For example, the emulsifier material in item 9 of the patent application scope is used in the field of emulsification of cosmetics, pharmaceuticals, food, and industrial products.

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