TWI618573B - A quercetin type surfactant, its preparation method and application - Google Patents

Abstract

The invention prepares a natural quercetin type surfactant, and uses the quercetin and the diol compound to synthesize a quercetin derivative under an acidic catalyst, and is selected from the group consisting of polyethylene glycol, polyethylene oxide, and poly The polyoxyethylene ether segment of oxyethylene is subjected to ring-opening polymerization with a diacid or an acid anhydride compound to obtain a block copolymer having an ether group, and the quercetin derivative is esterified with a block copolymer having an ether group. The reaction, further hydrolyzed hyaluronic acid, and a series of natural quercetin-type surfactants are prepared by condensation reaction. By combining the hydrophobic quercetin with hydrophilic hyaluronic acid through a condensation reaction technology, the water solubility of the surfactant is greatly improved, and the dispersing ability, emulsifying ability, wettability, lubricity, and luster texture are excellent, and at the same time It has the characteristics of biodegradable and natural environmental protection, and can be widely used in related industrial applications such as dyeing, finishing, cosmetics, cleaning products, pharmaceuticals, food, industrial products such as emulsification, dispersion and wetting.

Description

Quercetin type surfactant, preparation method and application thereof

The invention prepares a natural quercetin type surfactant, which is obtained by biodegradable and non-toxic quercetin and a diol compound by polycondensation of a quercetin derivative under an acidic catalyst, and different molecular weights selected from the group consisting of: Polyethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene (PoE) polyoxyethylene ether segment and diacid, or anhydride compound are ring-opened to obtain block copolymerization with ether groups As a spacer, the quercetin derivative is esterified with an ether group-block copolymer, and then hydrolyzed hyaluronic acid is added to form a series of natural quercetin-type surfactants through condensation reaction. . By combining the hydrophobic quercetin with hydrophilic hyaluronic acid through a condensation reaction technology, the water solubility of the surfactant is greatly improved, and the dispersing ability, emulsifying ability, wettability, lubricity, and luster texture are excellent, and at the same time It has the characteristics of biodegradable and natural environmental protection, and can be widely used in related industrial applications such as dyeing, finishing, cosmetics, cleaning products, pharmaceuticals, food, industrial products such as emulsification, dispersion and wetting.

In recent years, due to the rapid development of industry, there have been two serious problems affecting human survival, one is the energy crisis and the other is environmental pollution. The energy crisis is mainly caused by the massive consumption of oil. The goods used by humans are over-reliant on petroleum raw materials, resulting in a shortage of petroleum energy. And because of the petroleum-based products, many are not easily decomposed naturally. A large amount of waste causes serious environmental pollution on the earth. In order to reduce this phenomenon, the treatment technology of pollutants, the engineering technology to reduce pollutants and the development of decomposable raw materials are highly valued.

Therefore, environmental protection and safety are the main driving forces for the future development of the surfactant industry. It is of great significance to carry out environmental safety assessments on the possible hazards of surfactant contamination, degradation performance and cumulative performance in the environment. It is generally believed in the prior art that cationic surfactants are relatively toxic and commonly used for sterilization; anionic surfactants have certain toxicity; nonionic surfactants are relatively less toxic, but some degradation products are highly toxic. It is often discarded after use and is likely to cause environmental pollution. Therefore, in addition to considering its interface activity and functionality, it is important to assess whether environmental pollution is caused when using surfactants.

Decomposable surfactants, also known as temporary surfactants or controlled half-lives, are initially defined as: acid, alkali, and salt after completion of their application. The action of heat or light can be broken down into a non-interfacial active substance or a type of surfactant that is converted into a new interfacial active compound. The polar terminal of the surfactant molecule and the hydrophobic chain often contain a weak bond with limited stability. The cleavage of the weak bond can directly destroy the interfacial activity of the molecule, which is commonly referred to as the primary decomposition of the surfactant. The decomposable surfactant can be generally classified into two types, an acetal type and a ketal type, depending on the decomposable functional group. Compared with general surfactants, decomposable surfactants have a better environmental concept, and such surfactants can eliminate some complicated situations. In recent years, people's understanding of decomposable surfactants has been deepened and developed. The magnitude of environmental impact and the speed of biodegradability Has gradually become a very important indicator to judge the quality of surfactants.

Under the trend of stable development in the world, surfactants provide an excellent environment for the development of related industries, and the structure, items, performance and technical requirements of products are also 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.

The object of the present invention is to use natural quercetin as a raw material and to modify it into a green environmentally friendly surfactant by using hyaluronic acid, in addition to reducing the surface tension, good wettability, and interfacial activity of emulsification and dispersion. It has low toxicity, biodegradability and is harmless to the human body.

Quercetin (QT) used in the present invention, also known as quercetin and pentahydroxyflavone, is the most widely distributed flavonoid compound in the plant kingdom, and is a reducing compound having a phenolic hydroxyl group, which is easily oxidized and has antioxidant activity. The role of antioxidants in antioxidation is that the phenolic hydroxyl groups of the antioxidant react with harmful free radicals to form a relatively stable semi-quinone free radical, thereby stopping the chain reaction of harmful free radicals, and the compound has multiple phenolic hydroxyl groups. It is determined by the highest activity or the most reductive phenolic hydroxyl group to determine the oxidant properties. Secondly, through its own reducing properties, it directly gives electrons the consumption of harmful free radicals. It has great potential for development in today's society where green chemistry and energy reuse are emphasized. .

As shown in the following chemical formula (1), the B ring of quercetin is conjugated with the C ring, so that the entire molecule of quercetin is in the same plane, and the hydroxyl groups on the three rings of quercetin have different antioxidant activities, and the ring A has The meta-phenolic hydroxyl group is substituted, the B ring has an ortho-phenolic hydroxyl group substitution, and the C-ring has a hydroxyl group at the three positions. The phenolic hydroxyl group on the B ring has the highest antioxidant activity and the A ring has the weakest antioxidant activity.

After dehydrogenation of the 4'-hydroxyl group of quercetin, a stable resonant semi-quinone free radical is formed. The 4'-OH activity of quercetin is the highest, and hydrogen is most easily extracted. This is mainly due to the adjacent quercetin B ring. The weak hydrogen bonding interaction between the hydroxyl groups, this additional conjugation stability and synergy enhances the activity of the 4'-hydroxyl group. The reactive oxygen radicals are hydroxyl radicals (‧OH), peroxyl radicals (‧OOH) and superoxide anion radicals (O ₂ ^-‧ ). O ₂ ^-‧ is the most active oxygenated free radical. It is easy to react with OH at different positions in quercetin. When O ₂ ^{-‧ reacts} with 3-OH on the C ring of quercetin, it directly forms quercetin dehydrogenation radical and peroxy hydroxy anion radical complex. Things. The main antioxidant mechanism of quercetin is to form a resonance-stable semi-quinone radical structure by reacting phenolic hydroxyl groups with free radicals, thereby stopping the chain reaction of harmful free radicals. The reaction of quercetin molecules to scavenge oxygenated free radicals R‧ can be expressed as: [Quercetin-OH]+R‧→[Quercetin-O‧]+RH

A quercetin-type surfactant of the present invention is a surfactant having a structure of the formula (I), Wherein L is a diol compound residue, G is a quercetin residue, and x is an acid anhydride or a repeating amount of a -CH ₂ - segment of the diacid compound, and has a value of from 1 to 20, wherein the diol compound is selected from the group consisting of a linear or branched diol compound having 2 to 20 carbon atoms, and n represents the number of repeating units of the polyoxyethyl ether segment, and the value is 10 to 5000, wherein m represents the number of repeating units of the hyaluronic acid segment, and the value thereof is 10~10000.

The present invention relates to a quercetin-type surfactant, wherein hyaluronic acid (HA) is also called uronic acid, glacial sugar carbonic acid, and is a negatively charged glycosaminoglycan, which is used in animal connective tissue. Containing a linear polysaccharide consisting of D-glucuronic Acid and N-acetyl-D-glucosamine disaccharide monomer, β-1,3,β- A polysaccharide obtained by polymerizing a 1,4 glycosidic bond and having no branching, wherein the hyaluronic acid of the present invention is derived from any one of a microorganism fermentation method, a chemical synthesis method, and an animal extraction method. Hyaluronic acid in the human body is distributed in the extracellular matrix (ECM) and the Pericellular Matrix. Hyaluronic acid has a high concentration in the extracellular matrix of the soft connective tissue. Biocompatibility is related to skin maturation, aging and wound healing. Under normal physiological conditions, 50% of the hyaluronic acid in the human body is present in the intracellular matrix of the skin, and hyaluronic acid will bind to the surface receptor (CD-44) on the surface of the fibroblast, thereby causing the cells to aggregate with each other. If there is a large amount of hyaluronic acid around the wound, it will bind to CD-44 in a large amount, and the cells can not connect with each other to produce anti-cell adhesion properties, and at the same time drive the movement and proliferation of keratinocytes, and accelerate the migration of interstitial cells around the wound. As well as balancing the synthesis, regular arrangement and deposition rate of nascent collagen, thereby reducing scar formation, small molecules of hyaluronic acid can regulate the ability of tissue angiogenesis. Hyaluronic acid has characteristics such as water retention and viscosity, and it has a spatially rigid spiral column structure due to hyaluronic acid molecules. A large amount of hydroxyl groups are present inside the column to generate strong hydrophilicity, and hyaluronic acid The three-dimensional structure locks its combined water molecules in its double-helix columnar structure, so that moisture is not easily lost. The water retention capacity can theoretically be as high as 500mL/g, making hyaluronic acid in cosmetic plastic surgery, soft tissue reconstruction, joint fluid supplementation, ophthalmology. There are considerable contributions to surgery, dentistry and wound repair. The chemical structure is as follows: Wherein m represents the number of repeating units of hyaluronic acid segments, and the value is from 10 to 10,000.

The quercetin-type surfactant is a quercetin derivative which is bio-decomposable and non-toxic to human body and is condensed under an acidic catalyst, and is selected from the group consisting of: Ring-opening polymerization of ethylene glycol (PEG), polyethylene oxide (PEO), polyoxyethylene (POE) polyoxyethylene ether segment with diacid or anhydride compound to obtain block copolymer with ether group As a spacer, a quercetin derivative is esterified with an ether group-containing block copolymer, and then hydrolyzed hyaluronic acid is added to form a series of natural quercetin-type surfactants by a condensation reaction. By combining the hydrophobic quercetin with hydrophilic hyaluronic acid through a condensation reaction technology, the water solubility of the surfactant is greatly improved, and the dispersing ability, emulsifying ability, wettability, lubricity, and luster texture are excellent, and at the same time It has the characteristics of biodegradable and natural environmental protection. It can be widely used in dyeing and finishing, cosmetics, cleaning products, pharmaceuticals, food emulsification and other related industrial applications. It has excellent industrial applicability and market substitution.

The quercetin type surfactant of the present invention can be widely applied to wetness in industry. Run and emulsifier, due to its smooth, oil-control, long-lasting, waterproof and glossy effects, has become increasingly important in pharmaceutical and cosmetic applications. Quercetin itself is water-insoluble and it is still inconvenient in practical applications. The research team has passed this water-insoluble quercetin via glycols, diacids or anhydrides and polyoxyethylene ether segments, and hyaluronic acid. After acid modification, it becomes a water-soluble polymer containing polyester. This series of polymers has excellent interfacial properties, including surface tension, foaming and wetting. In terms of application properties, this series of water-soluble polymers can be applied to acid dye-dyed nylon fibers as a leveling agent to increase the affinity with dyes and reduce the diffusion rate of dye-surfactant complexes.

The invention discloses a preparation method of a quercetin type surfactant, which is a product A, an acid anhydride or a diacid compound which is reacted with quercetin and a diol compound, and is selected from the group consisting of polyethylene glycol, polyethylene oxide and poly The product B of the oxyethylene ether segment reaction of oxyethylene, and the condensation of the product A with the product B to obtain the product C, and the product C is further reacted with hyaluronic acid to obtain a crude product. A reaction product of a biodegradable, non-toxic quercetin reacted with a diol compound, using a polyoxyethylene ether segment of a different molecular weight selected from the group consisting of polyethylene glycol, polyethylene oxide, and polyoxyethylene. The reaction product with an acid anhydride or a diacid compound serves as a spacer for linking a reaction product of hyaluronic acid and a rind with a diol, wherein the hyaluronic acid transmits hydrophobic quercetin and hydrophilicity by a condensation reaction technique The combination of hyaluronic acid greatly enhances water solubility and exhibits its own excellent characteristics, making it more widely applicable in industrial use, and further improving the efficiency of biodegradability.

The preparation of a quercetin-type surfactant of the present invention comprises the following synthetic steps (a) to (d): (a) reacting quercetin with a diol compound, and slowly adding a catalyst to a temperature of 80 to 200 ° C, The reaction is carried out for 1 to 8 hours, and then cooled to 50 to 110 ° C, and a base (for example, an alkali metal hydroxide, NaOH, or the like) is added. KOH) terminate the reaction, warm up to 120 ~ 200 ° C between the pumping and decompression to remove excess diol and water and maintain for 2 ~ 6 hours, to obtain product A; (b) will be selected from: polyethylene glycol, polyethylene oxide The polyoxyethylene ether of polyoxyethylene and the diacid or anhydride compound are esterified, placed in a bottle and heated to 30-80 ° C, and the acid anhydride compound and the polyoxyethylene ether are uniformly mixed, and then the catalyst is added, and the temperature is gradually raised to 110~200°C, reaction for 2~8 hours, product B is obtained; (c) product A and product B are placed in a reaction flask and heated to 80-200 ° C, and water is removed by water-flow evacuation to obtain a product. C; (d) product C and hyaluronic acid compound, reacted at 60 ° C ~ 100 ° C for 3 ~ 10 hours, a series of quercetin-type surfactant crude product, which is then filtered with ethanol as solvent The unreacted material was removed, and the upper layer of the filtrate was extracted again, and the solvent was removed using a vacuum concentrator to obtain a final product.

The invention provides a preparation of a quercetin type surfactant, wherein the catalyst is selected from the group consisting of titanium (IV) tetraisopropoxide, sulfuric acid, hydrochloric acid or a group thereof.

The synthesis reaction formula of a quercetin-type surfactant of the present invention is as follows: wherein the diacid or anhydride compound is exemplified by maleic anhydride, and the diol compound is exemplified by propylene glycol.

Structural analysis of the quercetin-type surfactant of the present invention:

(1) Infrared absorption spectrometer

Perkin-Elmer Spectrum One, CT, concentrated the quercetin-type surfactant product of the present invention, completely removed the solvent in a vacuum oven, and applied the product to the test bench with ATR to analyze and identify the functional groups of each synthesized product.

The test results are shown in Table 1 and Figure 1.

(2) Nuclear magnetic resonance spectroscopy

Nuclear Magnetic Resonance Spectroscopy (NMR), NMR is one of the instruments for identifying the structure of organic compounds from trace compounds. It is measured by electromagnetic radiation absorption in the radio wave region of 4 to 600 MHz, involving the process of nuclear absorption. For some nuclei, there are spin and magnetic moment properties. From the viewpoint of quantum mechanics, the Nucleus in each element has its magnetic spin quantum number represented by I. When ≠0, the nucleus will generate NMR signals in the magnetic field; conversely, if I=0, the nucleus will not generate NMR signals in the magnetic field. Therefore, when exposed to a strong magnetic field, the nucleus absorbs electromagnetic radiation, and the result of energy level splitting is induced by the magnetic field. By Fourier transform (Fourier Transform), the molecular structure can be further analyzed and determined. H-NMR analyzer detection signal is mainly ¹ H nuclei, each of which ¹ H nuclei in the ambient environment is not the same molecule, and therefore the position of the signal appear not the same, i.e., the chemical shift (Chemical Shifts, δ), Based on TMS (Tetramethylsilane), it is determined to be 0, and the ¹ H-NMR chemical shift is usually between 0 and 15 ppm.

The results of the nuclear magnetic resonance spectrum test of the synthetic product of the quercetin-type surfactant of the present invention using heavy water (D ₂ O) as a solvent are shown in Table 2.

Performance analysis of the quercetin-type surfactant of the present invention:

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. The result of this test is shown in Figure 2.

2. Determination of contact angle.

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) The sample solution is dropped on the test board, and the screen is calculated by the computer to display the contact angle value.

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

The result of this test is shown in Figure 3.

3. Foaming determination

Model KD-10, Daiei Kagaku Seiki MFG.Co.LTD., Japan, with Ross and Determined by the 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.

The result of this test is shown in Figure 4.

4. Fluorescence spectrometry

Fluorescence spectrometer: Aminco-Bowman Series 2 Luminescence Spectrometer, Thermo Spectronic, Model FA-357.

(1) Fine scale 0.0101g pyrene fluorescent reagent was dissolved in 500 ml 95% ethanol solution, 0.2 g of hydrazine-ethanol solution was weighed in a 100 ml beaker (A beaker), and the ethanol was dried at 50 ° C in an oven.

(2) Prepare 20 ml of different concentration of auxiliary solution in a 100 ml beaker (B beaker).

(3) Pour 20ml of the auxiliary solution in the B beaker into the beaker containing the fluorescing fluorescent reagent, and place it on the ultrasonic oscillator for 15 minutes.

(4) Measurement by a fluorescence spectrometer, Excitation wavelength: 335 nm, Emission wavelength: 350 to 450 nm.

The result of this test is shown in Figure 5.

5. 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.

The results of this test are shown in Figures 6-8.

The quercetin type surfactant of the invention has excellent dispersing emulsifying ability, wetting, lubricity, and improving luster texture characteristics, and has the characteristics of biodegradable natural environmental protection, and can be widely applied to dyeing and finishing, It has excellent industrial applicability and market substitution in related industrial applications such as cosmetics, cleaning products, pharmaceuticals, food, and industrial products.

Figure 1. FT-IR spectrum of the quercetin surfactant of the present invention

Figure 2. Surface tension diagram of the quercetin surfactant of the present invention

Figure 3. Contact angle diagram of the quercetin-type surfactant of the present invention

Figure 4. Foaming diagram of the quercetin-type surfactant of the present invention

Figure 5. Fluorescence spectrum of the quercetin surfactant of the present invention

Figure 6. Ratio of the first peak to the third peak of the quercetin surfactant of the present invention

Figure 7. Conductivity diagram of the quercetin surfactant of the present invention

Figure 8. Average distribution of initial particle size at 0 hours of concentration of 0.5% (w/w) of quercetin-type surfactant of the present invention

Figure 9. Average particle size distribution of the quercetin-type surfactant of the present invention at the 5th hour of concentration 0.5% (w/w)

Figure 10. The quercetin-type surfactant of the present invention acts as an emulsion for castor oil, and the emulsified particle size of the concentration of 0.5% (w/w) changes with time.

Figure 11. Interfacial potential map of the quercetin-type surfactant of the present invention as an emulsion of castor oil at a concentration of 0.5% (w/w)

Preparation of quercetin type surfactant

Use materials:

(1) Quercetin (Quercetin)

MF: C ₁₅ H ₁₀ O ₇ , Mw: 302.23 g/mol

structure:

(2) Propylene glycol (PG) (Propylene Glycol)

MF: C ₃ H ₈ O ₂ , Mw: 76.10 g/mol

structure:

(3) Hyaluronic Acid

MF: (C ₁₄ H ₂₁ NO ₁₁ )n

(4) Maleic Anhydride (MA)

MF: C ₄ H ₂ O ₃ , Mw: 98.06 g/mol

structure:

(5) Polyethylene glycol (PEG)

structure:

The polyoxyethyl ether segment has a molecular weight of: 2000, 4000, 6000, 8000, 10000 (g/mol) of polyethylene glycol (PEG).

(6) Titanium Isopropoxide

MF: [(CH _{3) 2} CHO] ₄ Ti, Mw: 284.26 g/mol

(7) Castor Oil

MF: C ₅₇ H ₁₀₄ O ₉ , Mw: 933.61g/mol

(8) Fluorescent reagent

芘 (Pyrene)

MF: C ₁₆ H ₁₀ , Mw: 202.26 g/mol

Preparation method of quercetin type surfactant of the invention

(1) Hydrolysis of hyaluronic acid

40.0 g of hyaluronic acid, 360.0 mL of deionized water and 18.72 g of sodium hydroxide were placed in a steel cylinder, and a hydrolyzed hyaluronic acid was obtained by using a computer dyeing machine (Laboratory Dyeing Machines Jumbo) at a constant temperature of 110 ° C for 12 hours.

(2) Quercetin-type surfactant synthesis step

The synthetic steps including (a) to (d) are as follows: (a): 1 mole of quercetin and propylene glycol 1 mole are placed in a four-reaction reaction flask equipped with a Teflon stir bar and a temperature control rod, and 1.00 g of contact is added. Titanium Isopropoxide was slowly heated to 120 ° C, reacted for 4 hours, and then cooled to 90 ° C. The reaction was terminated by adding 1.50 g of sodium hydroxide, and the temperature was raised to 120-140 ° C. Excess propylene glycol and water were removed and maintained for 4 hours to obtain product A; (b): 1 mole of polyethylene glycol (Mw: 2000, 4000, 6000, 8000, 10000) and 2 mole of maleic anhydride were placed in the reaction flask. The temperature was raised to 60 ° C, the maleic anhydride was uniformly mixed with polyethylene glycol, and 1.00 g of Titanium Isopropoxide was added to slowly raise the temperature to 150 ° C for 5 hours to obtain product B. (c): The product A and the product B are placed in a reaction flask and heated to 120 ° C, and the water is removed by a water flow to remove the external H tube and reacted for 3 hours to obtain a product C; (d): 1 mole product C and 1 mole of hyaluronic acid compound, reacted at 80 ° C ~ 90 ° C for 8 hours to obtain a series of quercetin-type surfactant crude products, this Then to suction filtration using ethanol as a solvent was removed unreacted, the upper layer was re-extracted filtrate, concentrated under vacuum to give the final product The solvent was removed machine.

The quercetin type surfactant of the present invention is mainly composed of quercetin, propylene glycol, polyethylene glycol (Mw: 2000, 4000, 60,000, 8000, 10000), maleic anhydride and hyaluronic acid in the experimental examples. In order to raw materials, the quercetin and propylene glycol are firstly condensed to modify the water solubility of quercetin, and then the polyethylene glycol is changed differently (oxyethylene ether) EO chain length and maleic anhydride are synthesized to form an etheric amphiphilic block. The copolymer is finally synthesized by synthesizing the two-stage reaction product and introducing hydrophilic hyaluronic acid to prepare a series of quercetin-type surfactants. The codes and compositions of the products synthesized by the present invention are shown in Table 1.

Structural Identification and Analysis of Quercetin-type Surfactant of the Invention

The structure of the quercetin-type surfactant molecule synthesized by the present invention is confirmed by (FT-IR), and the infrared spectrum analysis chart mainly determines the molecular structure because all molecules have some fixed amount of energy, resulting in bond stretching. And bending, while the atoms oscillate and shake, causing other molecules to vibrate, and a fixed molecule can only bend or vibrate at a specific frequency equivalent to a specific energy level. When a molecule is irradiated with infrared light, the vibrating key absorbs energy only when the frequency of the light is the same as the vibration frequency of the key.

Figure 1 shows the results of infrared FT-IR spectroscopy analysis of the products of the quercetin-type surfactant of the present invention, and Table 2 shows the characteristic absorption peaks corresponding to various functional groups of the synthetic quercetin-type surfactant product, and the results can be seen - The asymmetric stretching vibration of OH and -NH is in the position of 3708~3010cm ^-1 . The stretching vibration of NH group appears in this range. It overlaps with the stretching vibration of OH group, but the peak shape is sharp, and the number of absorption peaks is on the nitrogen. For the number of hydrogen atoms; -CH ₂ asymmetric stretching vibration of 2912 ~ 2882cm ^-1; C = O stretching vibration of the 1770,1680cm ^-1 position; C = C a benzene ring skeleton vibration of 1540 cm ^-1 in a position The position of the asymmetric bending vibration of -CH _{3 is} 2894~3066cm ^-1 ; the symmetric stretching vibration absorption of CO is at the positions of 1141cm ^-1 , 1288cm ^-1 and 1291cm ^{-1 respectively} ; the out-of-plane bending vibration of CH is absorbed in 978cm ^-1 , 854cm ^-1 place.

The results of nuclear magnetic resonance spectroscopy (NMR) test analysis of the quercetin-type surfactant of the present invention using heavy water (D ₂ O) as a solvent are shown in Table 3, wherein δ = 0.8 to 1.1 ppm is CH ₃ ; δ = 3.3 ~4.2ppm is -CH ₂ ; δ = 3.7~4.5ppm is CH ₂ CH ₂ O; δ=4.8ppm is D ₂ O; δ=6.0~8.5ppm is CH ₂ =CH ₂ , which is higher than the hydrogen atom of general olefins It is also in the Down Field because the electron ring of benzene produces an Induced Magnetic Field, which makes the induced magnetic field required for protons weak.

Surface tension of quercetin-type surfactant of the present invention

When the surfactant is added to the aqueous solution, the surface tension is lowered. Since the surfactant itself contains a hydrophilic group and a hydrophobic group, the hydrophilic group in the solution will remain in the water, and the hydrophobic portion will adsorb the water surface. Caused by the arrangement. Such an arrangement reduces the asymmetric hydrogen bonding force of water molecules on the surface, and reduces the surface free energy, thereby causing a decrease in surface tension.

Assuming a temperature of 25 ° C at room temperature, the surface tension value is about 72.8 mN / m, and as the concentration of the surfactant increases, the surface tension value decreases. When the concentration increase reaches a certain level, the surfactant molecules begin to attract and aggregate with the hydrophobic groups in the solution to form the micelles. When the micelles start to form, the concentration is called the critical microcell concentration (Critical Micelle Concentration; CMC). ). Figure 2 shows the surface tension diagram of a series of quercetin surfactants of the present invention at different concentrations, in the order of QP2H<QP4H<QP8H<QP10H<QP6H, it can be explored that not all surfactants follow EO The chain increases the surface tension and thus rises, a series of products follow the EO chain The stronger the ability to reduce the surface tension is, the difference between the hydrophilic end and the hydrophobic end of the surfactant may be different due to the change of the raw material, and the balance of the two ends also shows the best interface properties. When the hydrophilic EO chain is too long and reaches the equilibrium of the hydrophobic end, the QP6H, QP8H and QP10H products increase the hydrophilicity of the product structure in water, resulting in an increase in surface tension, which in turn shows the highest surface with the product of QP6H. The tension value is more due to the hydrophilic EO chain length and the hydrophilic base portion than QP8H and QP10H.

When the surface concentration is larger, it indicates that the amount of surfactant molecules adsorbed on the liquid surface has reached saturation state, and the excess surfactant molecules will produce more micelles in the solution, while Table 4 is in the quercetin-type interface. The surface concentration of the active agent is (QP2H>QP8H>QP6H>QP4H>QP10H). In contrast, the smaller the over-surface area (Acmc), the less the surfactant molecules that can be adsorbed per unit area, the denser the interface of the solution, the smaller the interface, the more molecules are adsorbed, and the surfactant molecules will fold back into the solution to form micelles. .

Contact angle of quercetin type surfactant of the present invention

Surfactants have the ability to reduce the surface tension and free energy of liquids, so they are wettable. The wettability of the liquid on the solid surface can be judged by the size of the contact angle.

The invention compares the contact angle of the quercetin-type surfactant with the test plate by using different test plates as the wet object, and FIG. 3 is the contact angle of the concentration 1wt% QPH quercetin-type surfactant, which can be obviously obtained from FIG. It is known that the contact angle of water is different from the contact angle of the synthesized quercetin-type surfactant, the contact angle decreases as the chain of the EO chain length increases, and the contact angle of the quercetin-type synthetic product is (QP4H>QP6H >QP10H>QP8H>QP2H). The contact angle of the quercetin-type synthetic product is minimum QP4H, which shows that the wetting effect of this series is the best, and the mode of molecular arrangement of the product pulls the gravity to the inside, so that the free energy of the liquid surface is reduced, the surface tension and the contact angle are Decrease, when the EO chain increases, it can form hydrogen bonds with water molecules. The longer the EO chain, the more hydrogen bonds are formed, the more energy is required to destroy these hydrogen bonds, which causes the properties to rebound, forcing the contact angle to rise.

Foaming property of quercetin-type surfactant of the present invention

Pure water does not foam, and liquids of two or more components must be present to foam. The foam (Foam) is formed by agglomeration of bubbles, which are separated from each other by a solid film or a liquid film. In terms of the surfactant, the foam is generated at a moment when the hydrophobic group of the surfactant is directed toward the inside of the bubble, and the hydrophilic group faces the absorbing film of the solution phase to form a liquid film having elasticity. Surfactants are generally added to the liquid, which reduce the surface tension of the bubbles and form an elastic protective film between the bubbles.

It can be seen from FIG. 4 that the quercetin-type surfactant synthesized by the present invention has a foaming value of about 0.2 to 2.0 cm, which shows low foaming property and foam stability, and is more general anionic or Nonionic surfactants are low. The main reason is that the hydrophilic group and the hydrophobic group in the structure of the quercetin-type surfactant are arranged in a disorderly manner, and it is not easy to be arranged neatly and tightly around the bubble, that is, it is difficult to form a stable elastic film at the interface. Therefore, when the bubble is generated, it is quickly destroyed, so the foaming property is low. The foaming property of the quercetin-type surfactant of the present invention is shown in Figure 4, showing the foaming height: QP2H>QP4H>QP6H>QP8H>QP10H, and the foaming effect increases as the product polyoxyethylene (EO) chain length increases. The worse, the reason is that when the bubble is generated, the water film layer is highly hydrophilic and the EO molecular chain is in a carbonized state in the water, so that the intermolecular generation is arranged in a tightly arranged manner around the bubble, and it is difficult to form a stable interface. The elastic film is so quickly broken when bubbles are generated, so the foaming property is low.

Fluorescent properties of the quercetin-type surfactant of the present invention

In the micro- and micro-environment systems, the use of physical and chemical techniques in research has become an important issue. The use of fluorescent reagents (Pyrene) to confirm the unique affinity of molecular condensation, to explore the environmental impact of radioactivity, can also be used to describe the characteristics of microcell aggregation, the main spectroscopic instrument parameters include excitation and emission (Emission) spectral form, Fine vibration structure, quantum rate, and polarity in solution.

Figure 5 is a fluorescence spectrum of the quercetin-type surfactant of the present invention, showing that the change of the fluorescence intensity increases with the increase of the EO chain, and the result of the fluorescence intensity is (QP4H>QP6H>QP10H>QP8H>QP2H It can be found that the relative fluorescence intensity of QP8H and QP10H products is low. At this concentration, the formation of micelles causes the molecular agglutination speed to be earlier, which indirectly affects the fluorescence intensity. Figure 6 is a graph showing the ratio of the first peak to the third peak of the 0.1% by weight QPH quercetin type surfactant of the present invention. It is observed through the long graph that the product increases with the hydrophobic group and the ratio of the fluorescence intensity With the decrease, the QP4H ratio is larger and has a higher polarity, indicating that the product is more water-soluble.

Conductivity of the quercetin type surfactant of the present invention

Conductivity is an indicator of the amount of dissociated inorganic salts in water. Most inorganic acids, inorganic bases and salts dissociate in water to produce ions, which can be used as indicators of the concentration of metal salts in water, including anions (SO _{4 ).} ^2- , Cl ^- , NO _3- , CO ₃ ^2- , HCO ₃ ^- ) and cations (Ca ²⁺ , Mg ²⁺ , Na ⁺ , K ⁺ , Fe ³⁺ , Al ^{3+ ,} etc.). The conductive state is formed under a small amount of current, the anion tends to the anode, the cation tends to the cathode, and the conductivity of the solution is also related to the concentration of the anion and the cation in the solution and the spacing of the cation and the cation electrode, but some organic molecules are not easily dissociated in water, resulting in poor conductivity.

Generally speaking, the greater the conductivity value, the more the electrolyte content in the water, the increase of the charge leads to an increase in water hardness, and the surfactant molecules are not uniformly dispersed, resulting in agglomeration. The soft water conductivity is 0-200 μs/cm. The neutral water is 200~400μs/cm, and the hard water is more than 400μs/cm. The natural background of Taiwan's river surface water does not exceed 400μs/cm, but the conductivity is not specified in the discharge water standard. Conductivity is one of the important indicators for judging the quality of water used for irrigation. During crop growth, the osmotic pressure generated by conductivity affects the ability of crops to absorb water. Excessive metal ions are toxic to crops and produce salt to soil. Accumulation, the soil is salted and alkalized.

7 is a graph showing the conductivity of the quercetin-type surfactant of the present invention, wherein the conductivity value is between 0 and 200 μs/cm, and the conductivity of the quercetin-type surfactant is sequentially (QP2H). >QP6H>QP8H>QP4H>QP10H), the conductivity value should increase with the increase of EO chain length, but the conductivity of QP4H decreases. The reason may be that the hydrophilic group of the product is larger than the hydrophobic group, and the charge reaction in water is stronger. Therefore, the numerical value shows a downward trend. The test results show that the conductivity increases with the increase of the concentration of the auxiliary agent, and the value is in the range of soft water, indicating that it is not required to pass through the chelating agent if it is added to the special chemical. Pre-operation, which can reduce costs and is difficult Deterioration.

Emulsifying properties of the quercetin-type surfactant of the present invention

(1) Particle size analysis

The particle size of the emulsion is between 0.1 and 10 μm. When the particle size of the emulsion is too small, a collision occurs between the particles and the particles, which causes agglutination. The principle of this phenomenon is called Brownian Movement. On the other hand, when the emulsified particles are too large, sedimentation may occur to cause clogging or sedimentation.

The emulsified particle size analysis of castor oil is used in the present invention, and the quercetin type surfactant is used as an emulsion of castor oil, and the initial average particle size distribution of the 0th hour at a concentration of 0.5% (w/w) can be observed in FIG. The average particle size of the emulsion of QP2H is small. After 5 hours, it can be seen from Fig. 9 that the QP2H product emulsion still has a single-peak particle size curve with a smaller average particle size and an emulsion of the product. The surface adsorbs a layer of long-chain polymer, which produces a gate-off effect, resulting in a steric effect, and the hydrophilic group of hyaluronic acid is negatively charged. The surface of the particle is negatively charged, and the surrounding area attracts more positive electricity to form an electric double. The thicker the thickness of the electric double layer, the more stable it is and the less likely it is to agglomerate. Figure 10 is a quercetin surfactant used as an emulsion for castor oil. The emulsified particle size at a concentration of 0.5% (w/w) is analyzed with time. With the increase of time, the first two hours are thermodynamically unstable. The emulsion is rendered unstable and the particle size is increased. In contrast, the QP2H emulsion has a smaller tendency to change in particle size with time, indicating that the emulsion is relatively stable.

(2) Interface potential

When a general substance is in contact with water or other solvent, it will adsorb ions on the surface to generate surface charge, and the charge source is divided into two types. (1) The surfactant is an ion type, which itself dissociates to generate a charge, depending on its properties. The charge dissociated from the difference is also different, (2) is the surfactant is non- The ionic type is generated by the friction between the particles in the emulsion and the dispersion medium, and there is an electrostatic repulsion between the particles and the particles, so that the particles do not contact and aggregate with each other, so that the emulsion can be settled stably, and the emulsion is stable. The property can be analyzed by the interface potential (Zeta Potentials), which refers to the static voltage induced by the ions accumulated on the colloidal particles. One particle can derive the mobility of the electrophoresis by Henry's Equation, and then determine the interface potential. The value of the colloidal particles is composed of two layers of electrons, including a fixed layer and a diffusion layer.

Figure 11 is the interface potential diagram of quercetin surfactant for emulsion of camphor oil, the concentration is 0.5% (w / w), in which the zeta potential of the emulsion decreases with the change from pH3 to pH11. QP2H and QP10H emulsions are less stable in alkaline environments.

The quercetin-type surfactant synthesized by the invention has a slightly weaker interfacial activity than the commercially available product, but its environmental hazard is more friendly than the commercially available product, so the synthesized surfactant can be assisted. Commercially available surfactants to reduce environmental pollution.

The features, contents, advantages and advantages of the present invention will be described in detail in the embodiments of the present invention, and the descriptions used herein are merely for the purpose of illustration and description. The scope of the invention in the actual implementation is limited to the scope of the attached list.

Claims (10)

a quercetin-type surfactant, which is a surfactant having the structure of the general formula (I), Wherein L is a diol compound residue, G is a quercetin residue, and x is an acid anhydride or a repeating amount of a -CH ₂ - segment of the diacid compound, and has a value of from 1 to 20, wherein the diol compound is selected from the group consisting of A diol compound having 2 to 20 carbon atoms, and n represents a polyoxyethyl ether segment repeating unit number, and has a value of 10 to 5,000, wherein m represents a repeating unit number of hyaluronic acid segments, and the value is 10 to 10,000. A quercetin-type surfactant according to claim 1, wherein the polyoxyethyl ether segment is selected from the group consisting of polyethylene glycol (PEG), polyethylene oxide (PEO), and poly Made up of oxyethylene (POE). A quercetin-type surfactant according to the first aspect of the invention, wherein the hyaluronic acid is derived from any one of a microbial fermentation method, a chemical synthesis method, and an animal extraction method. A method for preparing a quercetin-type surfactant as described in claim 1, wherein the product A, an acid anhydride or a diacid compound which is reacted with quercetin and a diol compound is selected from the group consisting of polyethylene glycol Polyethylene oxide, polyoxyethylene ether polyoxyethylene ether reaction product B, and then product A and product B are condensed to obtain product C, product C and then reacted with hyaluronic acid compound to obtain the product. The preparation method of the quercetin-type surfactant according to item 4 of the patent application scope includes the steps of synthesizing (a) to (d) as follows: (a) reacting quercetin with a diol compound, and adding a catalyst Slowly raise the temperature to 80~200°C, react for 1~8 hours, then cool to 50~110°C, add alkali to terminate the reaction, warm up to 120~200°C and pump off the pressure to remove excess diol and water for 2~6 hours. Obtaining product A; (b) esterifying a polyoxyethylene ether selected from the group consisting of polyethylene glycol, polyethylene oxide, polyoxyethylene, and an acid anhydride compound, and placing the mixture in a bottle to raise the temperature to 30 to 80 ° C to stir After the acid anhydride compound and the polyoxyethylene ether are uniformly mixed, the catalyst is slowly heated to 110 to 200 ° C, and the reaction is carried out for 2 to 8 hours to obtain the product B; (c) the product A and the product B are placed in a reaction flask and heated up to 80~200°C, and remove water by depressurization with water flow to obtain product C; (d) product C and hyaluronic acid compound, react at 60°C~100°C for 3~10 hours to obtain quercetin-type interfacial activity The crude product is obtained, and the unreacted material is removed by suction filtration using ethanol as a solvent, and the upper layer of the filtrate is extracted, and the solution is removed by using a vacuum concentrator. Obtain the final product. The preparation method of the quercetin type surfactant according to Item 4 of the patent application is characterized in that the catalyst for synthesis is selected from the group consisting of titanium (IV) tetraisopropoxide, sulfuric acid, hydrochloric acid or a group thereof. A dispersant material comprising the quercetin-type surfactant as a dispersion material according to any one of claims 1 to 3. The dispersant material of claim 7 is used in the field of fiber dyeing and finishing aids and inorganic nanometer powder dispersants. An emulsifier material comprising the emulsifier material as disclosed in any one of claims 1 to 3, which is used as an emulsifying material in cosmetics, pharmaceuticals, foods, and industrial products. A fixing agent comprising the quercetin-type surfactant according to any one of claims 1 to 3 as a fixing material.