TW202200530A - Preparation method and its application of resveratrol type surfactant - Google Patents

Abstract

The resveratrol-type surfactant of the present invention uses modified polyethylene glycol, modified resveratrol and sodium alginate as the main raw materials, and uses polyethylene glycol with good dispersibility as the hydrophilic segment and acid anhydride. Or the diacid compound reacts to synthesize the first-stage product A, then carries out a condensation reaction with resveratrol and formaldehyde to synthesize the second-stage product B, and then adds the first-stage product A and the second-stage product B to the alginic acid Sodium reaction is synthesized to obtain the final resveratrol-type surfactant product, and then the resveratrol-type surfactant product is used for coating.

Description

Preparation and Application of Resveratrol-Type Surfactant

The resveratrol-type surfactant of the present invention uses modified polyethylene glycol, modified resveratrol and sodium alginate as the main raw materials. The acid compound is introduced into polyethylene glycol with different EO chain lengths to synthesize modified polyethylene glycol. The second stage is the synthesis of hydrophobic groups: the condensation reaction of resveratrol and formaldehyde is carried out to obtain modified resveratrol. Two-stage products: modified polyethylene glycol and modified resveratrol react with sodium alginate to synthesize a series of green resveratrol-type surfactants.

In recent years, due to the rapid development of industry, there have been two serious problems affecting human survival, one is 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, degradation performance and accumulation performance in the environment caused by the contamination of surfactants. In the prior art, it is generally believed that cationic surfactants are more toxic and are often used for sterilization and disinfection; anionic surfactants have certain toxicity; non-ionic surfactants are relatively less toxic, but some degradation products are very toxic. , It is often necessary to discard after use, which is easy to cause environmental pollution. Therefore, when using surfactants, in addition to considering its interface activity and functionality, whether it will cause environmental pollution Evaluation is very important.

Decomposable surfactants are also known as temporary surfactants or surfactants with controlled half-live. A class of surfactants that can be decomposed into non-interface active substances or converted into new interface active compounds by the action of heat or light. Such surfactant molecules often contain weak bonds with limited stability between the polar end and the hydrophobic chain, and the cleavage of the weak bonds will directly destroy the interfacial activity of the molecule, which is commonly referred to as the primary decomposition of surfactants. 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 such surfactants can eliminate some complex situations. In recent years, people's understanding of decomposable surfactants has been deepened and developed. The size of the environmental impact and the speed of biodegradability have gradually become a very important indicator for judging the quality of surfactants.

Under the trend of stable global 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.

Global ambient air pollution is becoming more and more serious, posing a serious threat to human health. Fine airborne particles of fine particulate matter (PM2.5) show higher cytotoxicity than other coarse particles. In fact, apart from the fact that PM2.5 can cause cardiovascular or respiratory system damage, few studies have evaluated the adverse effects of PM2.5 on normal human skin. Obtaining ammonium nitrate (SNA) in sulfate is of great significance in explaining the formation of haze in China. It is very important because it is the main component of fine particulate matter (PM) and plays a key role in the deterioration of air quality. This study uses sodium alginate and resveratrol modified material to synthesize Resveratrol-type surfactant, used to coat to isolate external dust.

The resveratrol-type surfactant of the present invention uses modified polyethylene glycol, modified resveratrol and sodium alginate as the main raw materials, and uses polyethylene glycol with good dispersibility as the hydrophilic segment and acid anhydride. Or the diacid compound reacts to synthesize the first-stage product A, then carries out a condensation reaction with resveratrol and formaldehyde to synthesize the second-stage product B, and then adds the first-stage product A and the second-stage product B to the alginic acid Sodium reaction is synthesized to obtain the final resveratrol-type surfactant product, and then the resveratrol-type surfactant product is used for coating.

Resveratrol (trans-3,5,4'-trihydroxystilbene) is a polyphenolic compound with various potential benefits to human health, including antioxidant, anti-inflammatory, anticancer, neuroprotective, Cardioprotective and hepatoprotective effects, etc. Sodium alginate and resveratrol are biodegradable raw materials, which can be decomposed by nature and even used for the treatment of human skin. From this, it can be known that they are safe and environmentally friendly for the human body.

In the present invention, polyethylene glycol with good dispersibility (different EO chain lengths: PEG1000, 2000, 4000, 6000) is used as a hydrophilic segment and an acid anhydride or diacid compound is reacted to synthesize the first-stage product A, and then white Veratrol and formaldehyde are subjected to condensation reaction to obtain the second-stage product B, and then the first-stage product A and the second-stage product B are added to sodium alginate for reaction synthesis to obtain a series of resveratrol-type surfactant final products, The obtained resveratrol-type surfactant is also a biodegradable environment-friendly material, so the present invention is quite suitable for industrial application and conforms to the future development trend.

The resveratrol-type surfactant of the present invention is an interface with the structure of general formula (I) active agent,

式中n表示聚乙二醇重複單位數，其值為2~10000；m表示白藜蘆醇段之重複單位數，其值為1~1000之整數；z表示海藻酸鈉段之重複數量，其值為1~20之整數；y表示酸酐或二酸化合物中-CH₂-段之重複數量，其值為1~20之整數。

In the formula, n represents the number of repeating units of polyethylene glycol, and its value is 2 to 10000; m represents the number of repeating units of the resveratrol segment, and its value is an integer of 1 to 1000; z represents the repeating number of the sodium alginate segment, Its value is an integer from 1 to 20; y represents the number of repetitions of the -CH ₂ - segment in the acid anhydride or diacid compound, and its value is an integer from 1 to 20.

In the resveratrol-type surfactant of the present invention, the acid anhydride or diacid compound is selected from a linear or branched acid anhydride or diacid compound having 3 to 23 carbon atoms.

In the resveratrol-type surfactant of the present invention, the acid anhydride or diacid compound is selected from succinic acid, succinic anhydride, maleic acid, and maleic anhydride.

The preparation method of the resveratrol-type surfactant of the present invention uses polyethylene glycol with good dispersibility as a hydrophilic segment and an acid anhydride or diacid compound to synthesize the first-stage modified polyethylene glycol product A, Then carry out condensation reaction with resveratrol and formaldehyde to obtain the second-stage modified resveratrol product B, then add the first-stage product A and the second-stage product B to sodium alginate for reaction synthesis to obtain a series of resveratrol Atrol-type surfactant.

The preparation method of the resveratrol-type surfactant of the present invention comprises (a) to The synthetic steps of (c) are as follows:

(a) Synthesis of polyethylene glycol and acid anhydride or diacid compound

Polyethylene glycol and acid anhydride or diacid compound are placed in a reactor, then a catalyst is added, and the mixture is uniformly stirred and slowly heated to 30-100°C. After a constant temperature reaction at this temperature for several hours, a series of modified polyethylene glycol products A are obtained;

(b) Condensation reaction of resveratrol and formaldehyde

After adjusting resveratrol and formaldehyde in an ethanol solvent, the modified resveratrol product B is obtained by reacting at a temperature of 30-100 ° C for several hours;

(c) Synthesis of Resveratrol-Type Surfactant

The product A of step (a), the product B of step (b), and sodium alginate are synthesized, and then a catalyst is added, and the reaction is uniformly stirred and slowly heated to a temperature of 90-200 ° C for several hours to obtain a series of resveratrol Alcohol-based surfactant product.

Wherein, the catalysts in steps (a) and (c) are selected from at least one of titanium isopropoxide, sulfuric acid, and hydrochloric acid. Wherein the synthesis of step (c) is the final resveratrol-type surfactant product, and then the final resveratrol-type surfactant product is used for coating. Among them, polyethylene glycols with different EO chain lengths (PEG1000, PEG2000, PEG4000, PEG6000) were used as raw materials.

The preparation method of the resveratrol-type surfactant of the present invention, wherein the catalyst is selected from titanium (IV) tetraisopropoxide (titanium isopropoxide), sulfuric acid, hydrochloric acid, or any one of the group consisting of them.

The synthesis reaction formula of the resveratrol-type surfactant of the present invention is as follows: wherein the diacid or acid anhydride compound is succinic anhydride as an example, and polyethylene glycol (PEG1000, 2000, 4000, 6000) is used as a hydrophilic segment

The resveratrol-type surfactant of the present invention is used as a dispersant material, and can be used in the fields of fiber dyeing and finishing auxiliaries, dispersants of inorganic nano-powders and the like.

The resveratrol-type 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 and the like.

Determination of the basic properties of the resveratrol-type surfactant of the present invention:

1. Surface Tension Determination

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 pull The force is the surface tension. With the increase of the surfactant concentration, the surface tension value decreases. When the concentration increases to a certain extent, the surfactant molecules begin to attract and aggregate with each other in the solution to form micelles. The concentration of the micelles at the beginning of formation , which is called critical micelle concentration (Critical Micelle Concentration; CMC), and this tight arrangement pattern will reduce the gravitational attraction of the molecules on the surface of the solution being pulled inward, reducing the surface free energy of the liquid and reducing the surface tension. The addition of 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 inside of the liquid, this arrangement reduces the free energy of the solution surface.

Test using a digital hanging platinum plate (type) surface tension tester

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

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

(2) Wash the platinum piece with alcohol and pure water, and then use an alcohol lamp to burn the platinum piece to fiery red and hang it on the hook after cooling.

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

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

(5) Repeat the above steps 3 times to obtain the average value.

Surface tension test of resveratrol-type surfactant, the test results are shown in Figure 1.

2. Contact angle measurement

Under normal circumstances, the surface of the 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 the liquid is called the wetting phenomenon. Surfactants have the ability to reduce the surface tension and free energy of liquids, and can exhibit their wettability. The contact angle is also an instrument for judging the ability of a specific liquid to wet a solid surface. The tangent to the edge of the water droplet extends from the point of contact between the droplet and the solid, and the angle formed by this tangent 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.

Using a contact angle meter, FACE CA-5 contact angle meter, place a standard plate on the material table to be tested, suck the sample solution with a syringe, and control the size of the droplet to be 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 of different concentrations.

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

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

The contact angle diagrams of the resveratrol-type surfactants with the concentrations of 1wt%, 0.1wt% and 0.01wt% on glass, acrylic and Teflon plates, the test results are shown in Figure 2, Figure 3 and As shown in Figure 4, the contact angle image is shown in Figure 5, Figure 6, and Figure 7.

3. 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 or scale formation factors. The lower the conductivity, the less ions or conductive substances contained in the water, so the conductivity can be used as an indicator of water quality management.

When the electrolyte dissolves in water, it will dissociate into cations and anions. When the current wants 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. (Book) The conductivity is mostly used to measure the critical micelle concentration (CMC) of the ionic surfactant solution. Generally speaking, the conductivity of the solution should be proportional to the solute concentration. The present invention is an anionic-nonionic surfactant, which can not only study its critical micelle concentration (CMC), but also analyze the change of its hydrophobic chain on the conductivity.

The conductivity of the resveratrol-type surfactant concentration of 1wt%, 0.1wt%, and 0.01wt% was tested, and the results are shown in Figure 8.

4.COD chemical oxygen demand (Chemical Oxygen Demand)

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. The size of the COD value can indicate the amount of organic matter in the water. Under certain conditions, the amount of oxidant consumed by the oxidation of 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 all the water samples are oxidized, expressed in mg/L, the degree of contamination by reducing substances in the reaction water is also used as one of the comprehensive indicators of the relative content of organic substances.

According to the different 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 used by this type of COD analyzer is potassium dichromate method, which has high data accuracy. , which is less disturbed by the natural environment, and is the preferred method for measuring COD indicators. Chemical principle: The water sample to be tested, potassium dichromate, silver sulfate and concentrated sulfuric acid are mixed in a certain proportion and gradually heated to 175 °C for digestion. During this period, chromium ions are converted from VI to III valence as an oxidant. The color is changed, and the degree of color change has 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.

When the concentration of resveratrol-type surfactant was 1wt%, 0.1wt%, and 0.01wt%, its COD concentration was measured. Oxygen demand, as shown in Figure 9.

5. Particle size analysis of emulsified droplets

There are various particles in nature, which can be divided into gases, liquids and solids according to their shapes and properties. Among them, the solid particles are often referred to as powder particles. Furthermore, these particles are often dispersed in a gas, liquid or solid phase at the time of application. Some particles are closely related to the daily life of human beings, but are rarely noticed by people.

In industry, mineral pigments will show different shades of color due to the different thickness of particles; in medicine, the size of drug particles will affect the absorption rate in the human body and the speed of drug efficacy; in technology, the fineness of ceramic materials Affects product flexibility and workability. If nano-scale nickel powder is used as the reaction catalyst of rocket solid fuel, the combustion efficiency of the fuel can be greatly improved, and the combustion stability can be improved. In public health, the size of insecticide spray particles can affect the insecticidal effect and spatial diffusion effect.

Therefore, all manufacturers of particle-related products, such as pigments, coatings, pesticides, latex, suspensions, cosmetics, pharmaceuticals, cement, ceramics, metals, etc., need to measure the size of the particles to control the quality of the product. . In recent years, the requirements for powders and granules have increased the size of manufactured particles to the level of nanometers. Therefore, the method and technology of particle size determination are not only one of the key points in the field of particle research, but also a main axis of research.

For the resveratrol-type surfactant of the present invention, the coating and agglutination conditions can be inferred from the change of particle size. The particle size of the coated product is about 0.1-10 μm, and the particle size changes after several hours due to Brownian motion ( Brownian Movement), particles will collide with each other, resulting in agglomeration. When the particles are too large, the particles will settle and cause stratification (Creaming) or sedimentation (Sedimentation). Therefore, the particle size of the coating product should be Normal distribution can make it milky The stability of the chemical solution means that when the particle size is smaller and the distribution is narrower, it has better stability.

The resveratrol-type surfactant concentration is 0.5wt%, 1wt%, 2wt%, respectively, with soybean oil and castor oil as the particle size distribution of the emulsion, the particle size distribution curve of the test results, as shown in Figure 10~12 Show.

6. Evaluation of the coating rate of the resveratrol-type surfactant of the present invention

In order to evaluate the coating rate, first prepare 0.5% resveratrol-type surfactant and dissolve it with nitrate, add soybean oil and beat at 11,000 rpm for 20 minutes in a homogenizer to complete the preparation. Use a UV-Vis spectrophotometer to monitor the solution at 565 nm. Here, the nitrate concentration is fixed at 5g/mL, and the resveratrol-type surfactant concentration is 0.5wt%, 1wt%, and 2wt% to observe the difference in the coating rate. The results As shown in Tables 2-4. Coverage is calculated based on the following formula: Coverage = m ₂ /m ₁ × 100% where m ₁ represents the weight of nitrate initially added and m ₂ is the weight of nitrate embedded in the particle, which is based on the drug concentration Calculated from a standard curve with absorbance. Each experiment was performed in triplicate for each sample, and results were expressed as mean ± standard deviation.

Fig.1 Surface tension diagram of resveratrol-type surfactant

Fig. 2 Contact angle diagram of resveratrol-type surfactant with concentration of 1wt%, 0.1wt% and 0.01wt% on glass plate

Fig.3 Contact angle diagrams of resveratrol-type surfactants with concentrations of 1wt%, 0.1wt% and 0.01wt% on acrylic plate

Fig. 4 Contact angle diagrams of resveratrol-type surfactants with concentrations of 1wt%, 0.1wt% and 0.01wt% on Teflon plates

Fig.5 Contact angle images of resveratrol-type surfactant concentration 0.01% on glass, acrylic and Teflon plates

Fig.6 Contact angle images of resveratrol-type surfactant concentration 0.1% on glass, acrylic and Teflon plates

Fig.7 Contact angle images of 1% resveratrol-type surfactant on glass, acrylic and Teflon plates

Figure 8. Conductivity diagram of resveratrol-type surfactant concentration of 1wt%, 0.1wt% and 0.01wt%

Fig. 9 COD chemical oxygen demand diagram of resveratrol-type surfactant at concentrations of 1wt%, 0.1wt% and 0.01wt%

Fig. 10 Particle size curve of resveratrol-type surfactant with a concentration of 0.5wt%

Fig. 11 Particle size curve of resveratrol-type surfactant with a concentration of 1wt%

Fig. 12 Particle size curve of resveratrol-type surfactant with a concentration of 2wt%

Fig. 13, Fig. 14, Fig. 15 are the microscopic pictures of soybean oil coating with resveratrol-type surfactant concentration of 0.5wt%, 1wt% and 2wt% respectively

Figure 16, Figure 17, Figure 18, Figure 19 are the spectrograms of the resveratrol-type surfactants of SRP1000, SRP2000, SRP4000, and SRP6000, respectively: (a) The spectrogram before coating, (b) Spectral curve after coating

The preparation of the resveratrol-type surfactant of the present invention uses materials:

(1) Polyethylene glycol

structure:

(2) Succinic anhydride

structure:

(3) Ethyl acetate

structure:

(4) 4-Dimethylamino-pyridine

structure:

(5) Resveratrol (Resveratrol)

structure:

(6) Formaldehyde

structure:

(7) Ethanol

structure:

(8) Sodium alginate

(9) Sulfuric acid

Preparation of the resveratrol-type surfactant of the present invention

The following synthetic steps (a) to (c) are included:

(a) Synthesis of polyethylene glycol/succinic anhydride

1 mole of polyethylene glycol (1000, 2000, 4000, 6000) and 2 moles of succinic anhydride were placed in a four-necked reaction flask equipped with a magnet stirring and a temperature control rod, ethyl acetate was the solvent, 4-dimethylaminopyridine (DMAP) was used as a catalyst to react at a temperature of 70° C. for 6 hours to obtain a series of products A of modified polyethylene glycol (modified PEG).

(b) Synthesis of Resveratrol/Formaldehyde

Place resveratrol and formaldehyde in a molar ratio of 1:3 in a four-necked reaction flask equipped with a magnet stirring and a temperature control rod, and ethanol is used as a solvent to adjust the base first, and then react at a temperature of 70 ° C for 6 hours for modification. Product B of resveratrol (modified RSV).

(c) Synthesis of green sodium alginate/resveratrol surfactant

(a) product A and (b) product B, sodium alginate molar ratio of 1:1:1 molar were added to the reaction flask, sulfuric acid was a catalyst, and the reaction was performed at a temperature of 120 ° C for 3 hours to obtain sodium alginate/resveratrol alcohol solution, and use water flow pumping and decompression to remove water to an external H tube for 1 hour to obtain a resveratrol-type surfactant.

Coating of Resveratrol Type Surfactant

Configure 0.5% resveratrol-type surfactant and dissolve it with nitrate, add soybean oil and beat at 11,000 rpm for 20 minutes with a homogenizer to complete the coating.

Synthesis of Resveratrol Type Surfactant of the Present Invention

Using modified polyethylene glycol (PEG1000, PEG2000, PEG4000, PEG6000), modified resveratrol, and sodium alginate as the main raw materials, the first stage of hydrophilic group synthesis is to introduce succinic anhydride into polymers with different EO chain lengths. Modified polyethylene glycol is synthesized from ethylene glycol, and the second stage is hydrophobic group synthesis. The modified resveratrol is obtained by condensation reaction of resveratrol and formaldehyde, and finally the two-stage products: modified polyethylene glycol and modified resveratrol, and then reacted with sodium alginate to synthesize a series of resveratrol Veratrol-type surfactant.

The codes of the resveratrol-type surfactant products of the present invention are based on the products synthesized from polyethylene glycols with different EO chain lengths. ~71%, as shown in Table 1.

Surface tension of the resveratrol-type surfactant of the present invention

The surface tension of a series of resveratrol-type surfactants, as shown in Figure 1, from the pre-microcellular area to the completion of the microcellular area when there are different amounts of the surface tension of the product, the decrease in surface tension is obvious in SRP2000 when the concentration is from 0.0087% When changing to 0.0505%, the surface tension decreases significantly and changes sharply, because the micelles are about to start to form. At a concentration of 0.5%, the formation of micelles was observed, and the surface tension value was curved at this time, indicating that CMC had been formed, but when the concentration further increased beyond CMC, the micelles had been completed, showing a stable curve that did not reduce the surface tension, SRP1000 The surface tension value is 59.8mN/m, the surface tension value of SRP2000 is 52.2mN/m, the surface tension value of SRP4000 is 50.1mN/m, the surface tension value of SRP6000 is 46.3mN/m, and the surface tension value is SRP1000>SRP2000>SRP4000>SRP6000 , the range is 46.30~59.80mN/m. Can know the surface tension of SRP1000 The largest value represents the worst interfacial activity, and the smallest surface tension value of SRP6000 represents the best interfacial activity. It can be used in detergents, cosmetics or drug coating to obtain the best results.

Contact angle of the resveratrol-type surfactant of the present invention

In the present invention, glass plate, acrylic plate and Teflon plate are used as wet objects to test the contact angle of resveratrol-type surfactant products of SRP1000, SRP2000, SRP4000, SRP6000 and the test plate, as shown in Figure 2 and Figure 3 , Figure 4 is the contact angle diagram of a series of resveratrol-type surfactant products with concentrations of 1wt%, 0.1wt%, and 0.01wt% on glass, acrylic, and Teflon plates, respectively. Among the series of products, the contact angle with the glass plate is the smallest, which means that the product has the best wettability, and the contact angle with the Teflon plate is the largest, indicating that the product has poor wettability. However, the contact angle values decreased with increasing surfactant concentration.

Figure 2 is a contact angle diagram of a series of resveratrol-type surfactant products on a glass plate. From Figure 2, the contact angle of the products can be known (SRP1000>SRP2000>SRP4000>SRP6000), in which SRP6000 is used in The contact angle of 1 wt% is the smallest, indicating the best wetting effect.

Figure 3 is the contact angle diagram of a series of resveratrol-type surfactant products on the acrylic plate. From Figure 3, the contact angle of the products can be known (SRP1000>SRP2000>SRP4000>SRP6000) The contact angle of SRP6000 is the smallest at 1wt%, indicating that its wetting effect is the best.

Figure 4 is the contact angle diagram of a series of resveratrol-type surfactant products on Teflon plates. From Figure 4, the contact angle of the products can be known (SRP1000>SRP2000>SRP4000>SRP6000) The contact angle of SRP6000 is the smallest at 1wt%, indicating that its wetting effect is the best.

Figure 5, Figure 6, Figure 7 are the contact angle images of a series of resveratrol-type surfactant products with concentrations of 0.01%, 0.1%, and 1% on glass, acrylic, and Teflon plates, respectively. It can be seen from Figure 8 to Figure 10 that the higher the contact angle concentration of the resveratrol-type surfactant product, the larger the EO chain in the sample, and the smaller the contact angle, the better the wettability. Because Figure 5 shows that the contact angle value of different products on the glass plate increases with humidity, the contact angle is the smallest, and the wettability is the best. Comparing different EO chain lengths, the contact angle is SRP1000>SRP2000>SRP4000>SRP6000, but SRP6000 at a concentration of 0.01 %, 0.1% and 1% all have the smallest contact angle value than other products, and their wettability is the best. Figure 6 shows the contact angle values of different products on acrylic sheets. The contact angle values of SRP1000 and SRP6000 do not change much at different concentrations, indicating that SRP1000 and SRP6000 have better stability to acrylic sheets. Comparing the contact angle values of acrylic sheets at concentrations of 0.01%, 0.1% and 1% for products with different EO chain lengths, it is shown that SRP6000 has the smallest contact angle value, indicating that SRP6000 has better wettability to acrylic sheets. Figure 7 shows the contact angle values of different products on Teflon plates. The contact angle values of SRP1000 and SRP6000 at different concentrations do not change much, indicating that SRP1000 and SRP6000 have better stability to Teflon plates. Comparing the contact angle values of Teflon plates with different EO chain length products at concentrations of 0.01%, 0.1% and 1%, it is shown that SRP6000 has the smallest contact angle value, indicating that SRP6000 has better wettability to Teflon plates.

Conductivity of the resveratrol-type surfactant of the present invention

The present invention can not only explore its critical micelle concentration (CMC), but also analyze the size change of its hydrophobic chain to conductivity. A series of resveratrol-type surfactant products of the present invention have concentrations of 1wt% and 0.1wt% respectively. %, 0.01wt% conduct conductivity detection, the results are shown in Figure 8, it is known that the conductivity value of a series of products of the present invention is between 0-400 μs/cm, with the concentration of resveratrol-type surfactant increases and the conductivity increases, where the magnitude of the conductivity is SRP1000>SRP2000>SRP4000>SRP6000, the conductivity value of the product decreases with the increase of EO chain length.

The chemical oxygen demand of the resveratrol-type surfactant of the present invention

The COD diagrams of a series of resveratrol-type surfactant products of the present invention, the concentrations are 1wt%, 0.1wt%, 0.01wt% respectively, chemical oxygen demand is detected, the results are shown in Figure 9, with the resveratrol With the increase of the concentration of alcohol-based surfactants, the chemical oxygen demand increases significantly. The COD value of SRP1000 at 0.1wt% is the highest, which means that more oxidants are needed to consume. A series of resveratrol-based surfactants of the present invention The COD value of the product is SRP1000>SRP4000>SRP6000>SRP2000, and SRP2000 has the smallest COD value at 0.1wt%. The chemical oxygen demand of the product of the present invention and the commercially available surfactants are discussed. The chemical oxygen demand of the product of the present invention is lower than that of a commercial nonionic surfactant, TX-100, but is lower than that of another commercial anionic surfactant. The SDS is high, because the raw material resveratrol in this study has a benzene ring structure and requires more oxidants for digestion. It is known that the resveratrol-type surfactant can be changed into a green and environmentally friendly interface activity through improvement. agent.

Particle size analysis of the resveratrol-type surfactant of the present invention

Fig. 10, Fig. 11, Fig. 12 are the particle size curves of resveratrol-type surfactants coated with soybean oil at concentrations of 0.5wt%, 1wt%, and 2wt%. It can be seen from the figures that the particle size of different concentrations The curve shows that the particle size decreases with the increase of the concentration, and it is less stable when the concentration is lower. When the concentration is 2wt%, the particle size curve of each product coated with soybean oil changes. When the particle size is smaller and the distribution is narrower It has better stability. Figure 10 shows that when the concentration is 0.5%, the particle size is SRP1000>SRP2000>SRP4000>SRP6000, SRP6000 has a smaller particle size, but has a particle size distribution greater than 6 μm , indicating that it is not enough. stability. Figure 11 shows that when the concentration is 1%, the particle size is SRP6000>SRP2000>SRP4000>SRP1000, SRP1000 has a smaller particle size, but the particle size distribution curve of SRP4000 is the narrowest, indicating that SRP4000 has better particles at 1% Uniformity and stability, Figure 12 shows the particle size distribution curve when the concentration is 2%, Figure 12 shows that the particle size distribution is in a stable state, and there is no uneven particle size. The particle size is SRP4000>SRP1000>SRP6000 >SRP2000, SRP2000 has a smaller particle size curve, showing that SRP2000 has the best emulsion stability at a concentration of 2%.

Fig. 13, Fig. 14, Fig. 15 are the micrographs of the coating of soybean oil by the resveratrol-type surfactant of the present invention at concentrations of 0.5wt%, 1wt%, and 2wt%, respectively. It can be seen from Fig. 13 that the concentration of 0.5 wt% The micrograph of wt% shows that the interior of the emulsion is not stable enough and there are flakes, indicating that the coating has not been completed. SRP6000 is relatively completely coated with particles. It can be seen from Figure 14 that the micrograph with a concentration of 1wt% shows SRP1000 Compared with SRP2000 and SRP4000, the particle state of SRP1000 and SRP6000 is smaller and more average. It can be seen from Figure 15 that the micrograph with a concentration of 2wt% shows that the particle state of SRP2000 compared with other products, SRP2000 is smaller and has no particle state. flaky condition.

Evaluation of the coating ratio of the resveratrol-type surfactant of the present invention

Table 2, Table 3 and Table 4 are the coating rates of resveratrol-type surfactants with concentrations of 0.5wt%, 1wt%, and 2wt%. The coating numbers are C-SRP1000, C-SRP2000, C-SRP4000, For C-SRP6000, it can be seen that the coverage rate is slightly improved with the higher concentration. It can be seen from Table 2 that the coverage rate of SRP2000 with a concentration of 0.5wt% is better than that of other products. It can be seen that the coverage rates of SRP2000 and SRP4000 with a concentration of 1wt% are equal, and the two coating states are better than others. It can be seen in Table 4 that the coverage rate of SRP4000 with a concentration of 2wt% is better than other products. . And in Table 2 to Table 4, 2wt% improved C-SRP4000 coating rate is the best.

Figure 16, Figure 17, Figure 18, Figure 19 are SRP1000, SRP2000, The spectrograms of SRP4000 and SRP6000 resveratrol-based surfactant products before (A) and after coating (B), the top picture (A) is the spectrogram before coating, the bottom picture (B) It is the spectroscopic curve after coating. In Figure 16 to Figure 19 (A), it can be clearly seen that there is no absorbance before coating, and Figure 16 (B) shows that after coating, there is a maximum absorbance at 565 nm, and the absorbance increases with the concentration of C-SRP1000 When the concentration is 2%, there is the best coating effect and obvious change. Figure 17(B) shows that after coating, there is a maximum absorbance at 565 nm, and the best coating is obtained when the absorbance increases with the concentration of C-SRP2000 at 1%. Figure 18(B) shows that after coating, the maximum absorbance is at 565 nm, and the absorbance increases with the increase of C-SRP4000 concentration. At 2%, there is the best coating effect and obvious change. Figure 19(B) shows that after coating, the maximum absorbance is at 565 nm, and the best coating is obtained when the absorbance of C-SRP6000 is increased at a concentration of 0.5%.

Table 4 Resveratrol type surfactant concentration 2wt% as coating rate

In the present invention, resveratrol is modified, and finally sodium alginate is added with polyethylene glycol with good dispersibility as a hydrophilic group segment for synthesis reaction to obtain a series of (SRP1000~SRP6000) resveratrol-type surfactants.

Through experimental analysis, the resveratrol-type surfactant product synthesized by the present invention has the property of reducing the surface tension as the concentration increases, and the resveratrol-type surfactant product of the present invention is measured and analyzed to obtain a procellular concentration of 0.05%. , the surface tension value ranges from 46.30 to 59.80 mN/m, and the lowest critical micelle concentration is obtained with the resveratrol-type surfactant product of SRP6000.

The contact angle test results of two series of synthetic products were analyzed. The contact angle of synthetic products to glass plate (Glass), acrylic plate (Acrylic Sheet) and Teflon plate (Telfon), among which the wettability of glass plate (Glass) was used. The best, followed by acrylic sheet (Acrylic Sheet), with the higher the concentration and the EO chain in the product, the wettability is relatively better, and the resveratrol-type surfactant product of SRP6000 is used on the glass plate. The best of (Glass).

The COD chemical oxygen demand test results of a series of products are all lower than the commercial TX-100 surfactant, indicating that it is relatively friendly to the environment, but because of the benzene ring structure, it requires more oxidizing agent than SDS surfactant. Digest.

From the particle size chart, it can be clearly observed that there is a forming effect from flake to spherical, and it is known that the coating part is successful, but the coating rate is about 44%, and there is no obvious difference in the change of concentration.

Claims (10)

A resveratrol-type surfactant, the surfactant having the structure of general formula (I),

In the formula, n represents the number of repeating units of polyethylene glycol, and its value is 2 to 10000; m represents the number of repeating units of the resveratrol segment, and its value is an integer of 1 to 1000; z represents the repeating number of the sodium alginate segment, Its value is an integer from 1 to 20; y represents the number of repetitions of the -CH ₂ - segment in the acid anhydride or diacid compound, and its value is an integer from 1 to 20. A resveratrol-type surfactant as claimed in item 1 of the patent application scope, wherein the acid anhydride or diacid compound is selected from linear or branched chain acid anhydride or diacid compounds with 3 to 23 carbon atoms. A resveratrol-type surfactant as claimed in item 1 of the patented scope, wherein the acid anhydride or diacid compound is selected from succinic acid, succinic anhydride, maleic acid, and maleic anhydride. A method for preparing a resveratrol-type surfactant according to any one of items 1 to 3 of the scope of the patent application, using polyethylene glycol with good dispersibility as a hydrophilic segment and an acid anhydride or a diacid compound to synthesize it. The first-stage modified polyethylene glycol product A is then subjected to a condensation reaction with resveratrol and formaldehyde to obtain the second-stage modified resveratrol product B, and then the first-stage product A and the second-stage product B are regenerated. A series of resveratrol-type surfactants were obtained by adding sodium alginate for reaction synthesis. Such as the preparation method of the resveratrol-type surfactant as claimed in the 4th item of the patented scope, comprising (a) The synthetic steps to (c) are as follows: (a) Synthesis of polyethylene glycol-acid anhydride or diacid compound Polyethylene glycol and acid anhydride or diacid compound are placed in a reactor, then a catalyst is added and slowly heated to 30-100 ° C with uniform stirring. After a constant temperature reaction at this temperature for several hours, a series of modified polyethylene glycol products A are obtained. ; (b) Synthesis of Modified Resveratrol/Formaldehyde The modified resveratrol product B is obtained by reacting resveratrol and formaldehyde in ethanol as a solvent, and then reacting at a temperature of 30-100 ° C for several hours; (c) Synthesis of green sodium alginate/resveratrol surfactant The product A of step (a), the product B of step (b), and sodium alginate are reacted, a catalyst is added, and the reaction is uniformly stirred and slowly heated to a temperature of 90-200 ° C for several hours to obtain a series of resveratrol-type Surfactant product. For the preparation method of resveratrol-type surfactant as claimed in item 4 of the patent application scope, the catalysts in steps (a) and (c) are selected from: titanium isopropoxide (titanium isopropoxide), sulfuric acid (Sulfuric acid), At least one of hydrochloric acid. Such as the preparation method of the resveratrol-type surfactant in the 4th item of the patent application scope, wherein. For the final product, the final product is used for coating, and the polyethylene glycol changes with different EO chain lengths. A dispersant material, comprising the resveratrol-type surfactant according to any one of items 1 to 3 of the application patent scope, and the prepared resveratrol-type interface according to any one of items 4 to 7 The active agent is a material, which is used in the field of fiber dyeing and finishing auxiliaries and dispersants of inorganic nano-powders. An emulsifier material comprising the resveratrol-type surfactant according to any one of items 1 to 3 of the patent application scope, and the prepared resveratrol-type interface according to any one of items 4 to 7 The active agent is the material. For example, the emulsifier material of item 9 of the scope of the application is used in the field of emulsification of cosmetics, pharmaceuticals, food, and industrial products.

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