CN115287061B - Preparation method of water-soluble ultraviolet absorbent, water-soluble ultraviolet absorbent and application thereof - Google Patents
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Abstract
The invention provides a preparation method of a water-soluble ultraviolet absorbent, which comprises the following steps: flavonoid biomass is used as a reaction raw material, an alcohol solvent is used as a reaction solvent, and a hydrothermal synthesis method is used for preparing a water-soluble ultraviolet absorbent; wherein the molecular structure of the flavonoid biomass meets the general formula I:the ultraviolet absorbent containing the carbon quantum dots can be prepared by the preparation method of the water-soluble ultraviolet absorbent, can efficiently absorb the full-band ultraviolet rays with the wavelength range of 280-400 nm (including UVB with the wavelength of 280-320 nm and UVA with the wavelength of 320-400 nm), and has good water solubility.
Description
Technical Field
The patent belongs to the technical field of ultraviolet absorber synthesis, and in particular relates to a preparation method of a water-soluble ultraviolet absorber, the water-soluble ultraviolet absorber and application thereof.
Background
Since ultraviolet rays are a part of sunlight, most of the ultraviolet rays are blocked by the ozone layer, but lower-energy UVA (with the wavelength of 320-400 nm) and UVB (with the wavelength of 280-320 nm) can penetrate through the ozone layer to reach the ground, the ultraviolet rays can enable free radicals to be generated in the high-molecular material, and finally the high-molecular material is degraded. In addition, this portion of the ultraviolet light may cause degradation of dyes, paints, and the like. For the human body, if exposed to ultraviolet rays of the wavelength band for a long period of time, it may cause damage such as optical keratitis, cataract, and ocular surface squamous tumor. It can be seen that both the polymer material and the human body are irreversibly damaged by long-term exposure to ultraviolet rays.
There are two types of ultraviolet absorbers currently on the market, organic ultraviolet absorbers and inorganic ultraviolet absorbers. Among them, most common organic ultraviolet absorbers are oil-soluble, and only two kinds of organic ultraviolet absorbers which can be dissolved in water are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP-4) and 2-phenylbenzimidazole-5-sulfonic acid (UV-T) on the market, and the organic ultraviolet absorbers have the defects of narrow absorption range, high toxicity and high price, and are difficult to popularize in a large scale in daily application. On the other hand, commercial inorganic ultraviolet absorbers mainly include zinc oxide, titanium oxide and other metal oxides, and the disadvantages of this type of ultraviolet absorber are low ultraviolet absorption efficiency, poor permeability, low light transmittance, poor dispersibility, high cost, and the like. Furthermore, this type of uv-screening agent has a poor affinity with organic materials and is difficult to mix with polymeric materials.
Based on the above, a water-soluble ultraviolet absorber which has good ultraviolet absorption effect and can be well compatible with polymer materials is sought, and the water-soluble ultraviolet absorber has important practical application significance.
Disclosure of Invention
The invention aims to seek a water-soluble ultraviolet absorbent with wide absorption range, high absorption efficiency and low price, a preparation method and application thereof.
According to one aspect of the present invention, there is provided a method for preparing a water-soluble ultraviolet absorber: flavonoid biomass is used as a reaction raw material, an alcohol solvent is used as a reaction solvent, and a hydrothermal synthesis method is used for preparing a water-soluble ultraviolet absorbent; wherein the molecular structure of the flavonoid biomass meets the general formula I:
preferably, the method comprises the steps of,r in the above general formula I 5 Or R is 6 At least one of which satisfies the general formula II:wherein R is 7 ~R 11 At least one of which is a hydroxyl group.
Preferably, R 7 ~R 11 Independently selected from hydrogen or hydroxy.
Preferably, the above formula II satisfies:
preferably, the above general formula I satisfies:
preferably, in the above formula I, R 1 ~R 4 Independently selected from hydrogen or hydroxy.
Preferably, the above general formula I satisfies:
preferably, the alcohol as the alcohol solvent is an alcohol having a main chain having less than 6 carbon atoms.
Preferably, the alcoholic solvent comprises one or more of ethanol, propanol, butanol.
Preferably, the alcohol solvent contains ethanol.
Preferably, the reaction temperature of the hydrothermal reaction is 200 to 240 ℃.
Preferably, the reaction time of the hydrothermal reaction is not less than 4 hours.
According to another aspect of the present invention, there is provided a water-soluble ultraviolet absorber prepared by the above-mentioned method for preparing a water-soluble ultraviolet absorber.
According to another aspect of the invention, the use of a water-soluble ultraviolet absorber as described above for the preparation of a sunscreen product and/or a paint product.
The ultraviolet absorbent containing the carbon quantum dots can be prepared by the preparation method of the water-soluble ultraviolet absorbent, can efficiently absorb the full-band ultraviolet rays with the wavelength range of 280-400 nm (including UVB with the wavelength of 280-320 nm and UVA with the wavelength of 320-400 nm), and has good water solubility. The water-soluble ultraviolet absorbent prepared by the method has high carbon content, wherein the carbon core surface of the carbon quantum dots contained in the water-soluble ultraviolet absorbent has benzene rings and aromatics, and the carbon quantum dots have more absorption peaks and wide distribution range, so that the carbon dots absorb ultraviolet rays with a wide ultraviolet range and ultraviolet rays with a wavelength of 280-400 nm. Compared with the existing ultraviolet absorbent, the carbon dot prepared by the invention has the advantages of wide ultraviolet absorption range, high absorption efficiency and high light transmittance, and particularly, the absorption rate of ultraviolet rays with the wavelength ranging from 340 nm to 400nm is obviously higher than that of the ultraviolet absorbent commonly used at present. The carbon dot surface hydrophilic groups prepared by the method are rich and can be dissolved in water; the carbon dots have high carbon content, the surfaces of the carbon cores are provided with unsaturated bonds and closed-loop conjugated system groups, the absorption peaks are more, the distribution range is wide, the ultraviolet absorption wave band range of the ultraviolet absorbent containing the carbon quantum dots is wide, and in addition, the ultraviolet absorbent prepared by the invention has two pi-pi absorption peaks with strong absorption, so that the ultraviolet absorbent can show high absorption capacity to ultraviolet rays, hardly absorbs visible light, has high visible light transmittance, and does not influence daily use.
Drawings
FIG. 1 is a graph showing the absorption and transmission of ultraviolet-visible light of the ultraviolet absorber B prepared in example 1;
FIG. 2 is an infrared spectrum of the ultraviolet absorber B prepared in example 1;
FIG. 3 is a transmission electron microscope image and a corresponding lattice fringe pattern of the ultraviolet absorber prepared in the treatment group 1B of example 2, wherein the left side is the transmission electron microscope image, and the right side is the lattice fringe pattern;
FIG. 4 is a graph showing the particle size distribution of the ultraviolet absorber produced in treatment group 1B of example 2;
FIG. 5 is a graph showing the optical properties of the ultraviolet absorber obtained in the treatment group 1B of example 2, wherein the left graph is an ultraviolet-visible light absorption spectrum, the transmission spectrum, and the right graph is an infrared absorption spectrum;
FIG. 6 is a graph showing the optical characteristics of the ultraviolet absorber obtained in the treatment group 2B of example 2, wherein the left graph is an ultraviolet-visible light absorption spectrum, the transmission spectrum, and the right graph is an infrared absorption spectrum;
FIG. 7 is a graph showing the optical properties of the ultraviolet absorber obtained in the treatment group 3B of example 2, wherein the left graph is an ultraviolet-visible light absorption spectrum, and the right graph is an infrared absorption spectrum;
FIG. 8 is a graph of the ultraviolet absorption spectrum of the ultraviolet absorber obtained in the treatment group 1B of example 2 compared with the ultraviolet absorption spectrum provided in the journal document, wherein the left graph is the ultraviolet absorption spectrum provided in the journal document, and the right graph is the ultraviolet absorption spectrum of the ultraviolet absorber obtained in the treatment group 1B of example 2;
FIG. 9 is a graph showing the comparison of the infrared absorption spectrum of the ultraviolet absorber obtained in the treatment group 1B of example 2 with the infrared absorption spectrum provided in the journal document, wherein the left graph is the infrared absorption spectrum provided in the journal document, and the right graph is the infrared absorption spectrum of the ultraviolet absorber obtained in the treatment group 1B of example 2;
fig. 10 is a comparison of XPS spectra of the ultraviolet absorber prepared in the treatment group 1B of example 2 with XPS spectra provided in journal literature, wherein (a), (B), and (c) are XPS spectra of the ultraviolet absorber prepared in the treatment group 1B of example 2, and (d), (e), and (f) are XPS spectra provided in literature 1.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
1. Preparation of ultraviolet absorbers
In this example, 6 treatment groups were set using different flavonoid biomasses as raw materials, and the raw materials used for each treatment group are shown in table 1.
TABLE 1 flavonoid Biomass species used in each treatment group of EXAMPLE 1
The processing groups take flavonoid biomasses corresponding to the processing groups as reaction raw materials, ethanol is used as a reaction solvent, and the ultraviolet absorbent is prepared by a hydrothermal method.
Treatment group 1A prepared an ultraviolet absorber as follows:
0.045g of luteolin is dissolved in 20mL of absolute ethyl alcohol to form a precursor solution, then the precursor solution is sealed in a polytetrafluoroethylene lining with the capacity of 50mL, and the polytetrafluoroethylene lining is placed in an oven with the temperature of 220 ℃ for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent A.
Treatment group 2A prepared an ultraviolet absorber as follows:
0.03g of quercetin was dissolved in 20mL of absolute ethanol to form a precursor solution, and then the precursor solution was sealed in a polytetrafluoroethylene liner having a capacity of 50mL, and put into an oven at 220℃for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent B.
Treatment group 3A prepared an ultraviolet absorber as follows:
0.04g of ginkgetin is dissolved in 20mL of absolute ethyl alcohol to form a precursor solution, then the precursor solution is sealed in a polytetrafluoroethylene lining with the capacity of 50mL, and the polytetrafluoroethylene lining is put into an oven with the temperature of 220 ℃ for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent C.
Treatment group 4A prepared the uv absorber as follows:
0.03g of soyabean extract is dissolved in 20mL of absolute ethyl alcohol to form a precursor solution, then the precursor solution is sealed in a polytetrafluoroethylene lining with the capacity of 50mL, and the polytetrafluoroethylene lining is placed in an oven with the temperature of 220 ℃ for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent D.
Treatment group 5A prepared the uv absorber as follows:
0.03g of locust booth was dissolved in 20mL of absolute ethanol to form a precursor solution, which was then sealed in a polytetrafluoroethylene liner having a capacity of 50mL, and put into an oven at 220 ℃ for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent E.
Treatment group 6A prepared the uv absorber as follows:
0.02g of naringin is dissolved in 20mL of absolute ethanol to form a precursor solution, then the precursor solution is sealed in a polytetrafluoroethylene lining with the capacity of 50mL, and the polytetrafluoroethylene lining is placed in an oven with the temperature of 220 ℃ for hydrothermal reaction for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product, namely an ultraviolet absorbent F.
2. Water solubility test
… … g of the solid ultraviolet absorbent finished product prepared in each treatment group of this example was weighed and added to … … mL of deionized water, and the resultant liquid sample was allowed to stand at room temperature for 2 days to observe the morphology of the liquid sample. The aqueous solution of the ultraviolet absorber to be tested was left to stand as follows: the liquid sample remained in a stable, uniform solution state, and no solid precipitation or delamination of the solution was observed.
3. Characterization of uv absorption properties:
(1) Reference sample
In different treatment groups, respectively taking a precursor solution and an ultraviolet absorbent prepared by the precursor solution through a hydrothermal method for ultraviolet absorption test, wherein the sample treatment method comprises the following steps: for the precursor solution, ultraviolet absorbance test can be directly carried out, and for the solid ultraviolet absorbent finished product, the ultraviolet absorbent finished product is firstly dissolved in water to prepare an aqueous solution, and ultraviolet absorbance detection is carried out on the aqueous solution dissolved with the ultraviolet absorbent; in the process of taking the samples, the mass of the precursor solution samples is the same, and the mass of the solid ultraviolet absorbers is the same.
(2) Data processing
In the detection of ultraviolet absorbance, the ultraviolet absorbance of a sample in two wave bands of 280-400 nm and 340-400 nm is counted, the ultraviolet absorbance of the sample in 280-400 nm is taken as C1, the ultraviolet absorbance of the sample in 340-400 nm is taken as C2, the ultraviolet absorbance ratio of the sample in a special wave band is represented by the ratio of C2 to C1 measured by the same sample, and the ultraviolet absorbance ratio of the special wave band can be used for realizing parallel comparison of the ultraviolet absorbance effects of different samples in the ultraviolet range of 340-400 nm.
The data test results are shown in table 2. The precursor solutions of each treatment group had relatively low ultraviolet absorptivity before the hydrothermal reaction, and the ultraviolet absorptivity of the products of each treatment group had been improved to a different extent after the hydrothermal reaction, thus indicating that the ultraviolet absorptivity of the ultraviolet absorbers produced by each treatment group did not result from the ultraviolet absorptivity of the raw materials themselves. Referring to the results of Table 2, the UV absorbers prepared in treatment groups 5A and 6A were significantly lower in UV absorbance at 340-400 nm than the other treatment groups, and from the structures of the raw materials used in each of the treatment groups shown in Table 1, it is clear that the structures of the raw materials used in treatment groups 1A-4A all conform to the general formula I:however, the material structures of the raw materials of the locust fruit and the olein used in the treatment group 5A and the treatment group 6A, respectively, do not conform to the above general formula i, and it can be said that in this embodiment, the material structures of the raw material reactants have a non-negligible key influence on the ultraviolet absorption performance of the finally produced ultraviolet absorber. In the treatment groups 1A to 4A, the ultraviolet absorption performance corresponding to the ultraviolet absorbent A and the ultraviolet absorbent B, especially the special wave band, which are respectively prepared by the treatment group 1A adopting luteolin and the treatment group 2A adopting quercetinThe ultraviolet absorption ratio of the ultraviolet absorber is obviously higher than that of ultraviolet absorbers prepared by other treatment groups.
TABLE 2 ultraviolet absorption Performance test results
Example 2
Based on the test results of example 1, the ultraviolet absorption performance of the ultraviolet absorber B prepared in example 1 using the treatment group 2A using quercetin was the best effect among all the reference ultraviolet absorbers, and this example will characterize the product performance of the ultraviolet absorber B prepared in example 1.
FIG. 1 shows the UV-visible absorption and transmission spectrum of UV absorber B, and it can be seen that the produced UV absorber B has three absorption peaks at 261nm, 290nm and 362nm, the absorption peak at 261nm being due to pi-pi transition of benzene rings attached to the surface of the carbon core; whereas the absorption peak at 290nm is due to pi-pi transition of aromatic clusters attached to the surface of the carbon core, the absorption peak at 362nm is due to n-pi transition of c=o. FIG. 2 is an infrared absorption spectrum of the ultraviolet absorber B, from which it can be seen that the ultraviolet absorber B is present at 3430cm -1 There is a broader absorption band due to the stretching vibration of-OH at 1650cm -1 The absorption peak at which is ascribed to C=O stretching vibration, 1480cm -1 The absorption peak at this point is attributed to the stretching vibration of the aromatic ring c=c.
Example 3
Based on the excellent ultraviolet absorption performance of the ultraviolet absorber B prepared in example 1, the ultraviolet absorber was prepared by a hydrothermal method using quercetin as a raw material, by changing a reaction solvent, setting different treatment groups.
Treatment group 1B an ultraviolet absorber was prepared in the manner employed in treatment group 2A of example 1.
Treatment group 2B the uv absorber was prepared in the manner described in reference to treatment group 2A of example 1, with propanol replacing the reaction solvent used in treatment group 2A, and other materials and operations were strictly consistent with treatment group 2A.
Treatment group 3B the uv absorber was prepared in the manner described in reference to treatment group 2A of example 1, with butanol replacing the reaction solvent used in treatment group 2A, and other materials and operations were strictly consistent with treatment group 2A.
The optical performance of the finished product obtained in the 3 treatment groups constructed in this example was characterized, in which the transmission electron microscope image and the lattice fringes of the ultraviolet absorber obtained in the treatment group 1B are shown in fig. 3, and the lattice fringes of the ultraviolet absorber sample particles are 0.21nm, so that it is explained that the ultraviolet absorber obtained in the treatment group 1B contains carbon quantum dots, and in addition, the particle size distribution diagram of the product obtained in the treatment group is shown in fig. 4. Specifically, fig. 5 to 7 show the same. By comparison, the ultraviolet absorbent prepared by adopting ethanol, propanol and butanol can generate effective ultraviolet absorption in the whole wave band of 280-400 nm, and particularly, the ultraviolet absorbent can generate high-intensity ultraviolet absorption effect in the wave band range of 340-400 nm.
In the journal literature (hereinafter referred to as "literature 1") Sustainable Carbon Dot-Based AIEgens, promising Light-Harvesting Materials for Enhancing Photosynthesis (Damine Xiao et al, ACS Sustainable chem. Eng.2021,9, 4139-4145), a scheme for preparing an ultraviolet absorber by a hydrothermal method using quercetin as a reaction raw material and water as a reaction solvent was proposed. Comparing the structure and performance characteristics of the product obtained in the treatment 1B of this example with those reported in literature 1, and referring to fig. 8 to 10, it can be seen that the apparent difference between the two can be clearly seen from comparison of the ultraviolet absorption spectrum (fig. 8), the infrared absorption spectrum (fig. 9) and the XPS spectrum analysis (fig. 10). Therefore, the flavonoid biomass selected by the scheme is used as a reaction raw material, the type of a reaction solvent can directly determine the performance of a product, and the prepared ultraviolet absorbent can only generate a high-intensity ultraviolet absorption effect within the wave band range of 340-400 nm by using an alcohol solvent as the reaction solvent.
Example 4
Based on the excellent ultraviolet absorption performance of the ultraviolet absorber B prepared in the example 1, the ultraviolet absorber is prepared by taking quercetin as a raw material and ethanol as a reaction solvent through a hydrothermal method at different hydrothermal temperatures. The specific operation is as follows:
0.03g of quercetin was dissolved in 20mL of absolute ethanol to form a precursor solution, the precursor solution was then sealed in a polytetrafluoroethylene liner having a capacity of 50mL, the reaction temperature was set in an oven (treatment group 1C,180 ℃ C.; treatment group 2C,195 ℃ C.; treatment group 3C,220 ℃ C.; treatment group 4℃,235 ℃ C.; treatment group 5℃,250 ℃ C.) and the precursor solution was subjected to hydrothermal reaction at the reaction temperature for 6 hours. After naturally cooling to room temperature, the stock solution was filtered with a filter membrane having a pore size of 0.22 μm to remove large particles, and then the supernatant was dialyzed with a dialysis bag having a molecular weight of 1000Da for 72 hours. And (3) carrying out rotary evaporation concentration on the dialyzed solution, pouring the concentrated solution into a beaker with the capacity of 25mL, and freeze-drying to obtain a final purified solid ultraviolet absorbent finished product.
The ultraviolet absorbers prepared in each treatment group of this example were subjected to ultraviolet absorption performance test by the method of example 1, and the test results are shown in table 3.
TABLE 3 ultraviolet absorption Performance test results
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a water-soluble ultraviolet absorbent is characterized in that: flavonoid biomass is used as a reaction raw material, an alcohol solvent is used as a reaction solvent, and the water-soluble ultraviolet absorbent is prepared by a hydrothermal synthesis method; wherein the molecular structure of the flavonoid biomass meets the general formula I:
wherein R is 1 ~R 4 Independently selected from hydrogen or hydroxy, R in formula I 5 Or R is 6 At least one of which satisfies the general formula II: />,R 5 Or R is 6 At least one of which is independently selected from hydrogen or hydroxy, R 7 ~R 11 Independently selected from hydrogen or hydroxy, and R 7 ~R 11 At least one of which is a hydroxyl group.
2. The method of preparing a water-soluble ultraviolet absorber according to claim 1, wherein the general formula ii is:。
3. the method of preparing a water-soluble ultraviolet absorber according to claim 1, wherein the general formula i satisfies:。
4. the method of preparing a water-soluble ultraviolet absorber according to claim 1, wherein the general formula i satisfies:。
5. the method for producing a water-soluble ultraviolet absorber according to claim 1, wherein the alcohol as the alcohol solvent is an alcohol having a main chain carbon number of less than 6.
6. The method of preparing a water-soluble ultraviolet absorber according to claim 1, wherein the alcohol solvent comprises one or more of ethanol, propanol, and butanol.
7. The method for preparing a water-soluble ultraviolet absorbent according to claim 1, wherein the reaction temperature of the hydrothermal reaction is 200-240 ℃.
8. A water-soluble ultraviolet absorber prepared by the preparation method of any one of claims 1 to 7.
9. Use of a water-soluble uv absorber as claimed in claim 8 in sun protection products and/or paint products.
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