CN117731545A - Method for stabilizing organic sun-screening agent butyl methoxy dibenzoyl methane - Google Patents
Method for stabilizing organic sun-screening agent butyl methoxy dibenzoyl methane Download PDFInfo
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- CN117731545A CN117731545A CN202311762973.4A CN202311762973A CN117731545A CN 117731545 A CN117731545 A CN 117731545A CN 202311762973 A CN202311762973 A CN 202311762973A CN 117731545 A CN117731545 A CN 117731545A
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- hydrotalcite
- butyl methoxy
- dibenzoyl methane
- ethanol
- methoxy dibenzoyl
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- TYYHDKOVFSVWON-UHFFFAOYSA-N 2-butyl-2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)(CCCC)C(=O)C1=CC=CC=C1 TYYHDKOVFSVWON-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229960005193 avobenzone Drugs 0.000 title claims abstract description 44
- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 8
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 42
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000000475 sunscreen effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002502 liposome Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000037072 sun protection Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 201000004624 Dermatitis Diseases 0.000 description 1
- 239000004378 Glycyrrhizin Substances 0.000 description 1
- 229920001144 Hydroxy alpha sanshool Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PSKIOIDCXFHNJA-UHFFFAOYSA-N Sanshool Natural products CC=CC=CC=CCCC=CC=CC(=O)NC(C)C PSKIOIDCXFHNJA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- SBXYHCVXUCYYJT-UEOYEZOQSA-N alpha-Sanshool Chemical compound C\C=C\C=C\C=C/CC\C=C\C(=O)NCC(C)C SBXYHCVXUCYYJT-UEOYEZOQSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 description 1
- 229960004949 glycyrrhizic acid Drugs 0.000 description 1
- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 description 1
- 235000019410 glycyrrhizin Nutrition 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical group C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 229960000601 octocrylene Drugs 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960001173 oxybenzone Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
Abstract
The invention discloses a method for stabilizing butyl methoxy dibenzoyl methane as an organic sun-screening agent. According to the method, more hydrotalcite oxygen vacancies are constructed by adjusting the roasting temperature and mode, then butyl methoxy dibenzoyl methane is loaded on hydrotalcite by utilizing the reconstruction effect of hydrotalcite, so that metal elements on a hydrotalcite laminate are coordinated with beta-diketone structures in the butyl methoxy dibenzoyl methane to form a stable six-membered ring structure, the light stability and chemical stability of the butyl methoxy dibenzoyl methane can be obviously improved through 'occupying a place in advance', the light degradation rate is reduced from 15.06% to 4.06% under the same dose of ultraviolet irradiation, other organic sunscreens are not needed to be added, and the human body and environmental safety of finished cosmetics are improved while the efficacy is ensured.
Description
Technical Field
The invention belongs to the field of personal care sunscreens, and particularly relates to a method for stabilizing an organic sunscreens butyl methoxy dibenzoyl methane (AVB).
Background
In real life, ultraviolet rays can be classified into three types of UVA (320-400 nm), UVB (280-320 nm) and UVC (200-280 nm), wherein UVC is almost absorbed by ozone layer, and UVA and UVB are mainly harmful to human skin. At present, consumers gradually realize the importance of sun protection, and the quality of sun protection agents directly influences the performance of sun protection products. In the technical Specification of cosmetic safety in China, sunscreens are divided into two major categories, namely organic sunscreens and inorganic sunscreens, wherein the organic sunscreens can achieve a sun-screening effect by absorbing ultraviolet rays by themselves, but can cause certain irritation to skin; the inorganic sun-screening agent titanium dioxide and zinc oxide can block ultraviolet rays through physical methods such as scattering and diffuse reflection, has low irritation, but has certain photocatalytic property, and is easy to generate free radicals to cause damage to skin.
Among them, butyl methoxy dibenzoylmethane (AVB) among organic sunscreens is one of the few UVA sunscreens which have been approved by FDA, has a good sunscreening effect, but has a photo-instability, and is easily deposited on the surface of laundry in daily use as a reddish brown complex with iron ions in tap water and sweat, affecting beauty. At present, the butyl methoxy dibenzoylmethane is usually used together with sunscreens such as benzophenone-3 or octocrylene, however, the introduction of new sunscreens increases the risk of skin allergy. Many researchers have focused on stabilizing butyl methoxydibenzoylmethane, but most of them are in the form of compositions, such as phosphate-based emulsifiers (CN 101945686A), sanshool or derivatives thereof (CN 115446536A) used together with butyl methoxydibenzoylmethane, while being able to enhance the stability of butyl methoxydibenzoylmethane and having good ultraviolet absorption properties, the introduction of more organic matters undoubtedly increases the safety risk of the product, and cannot fundamentally solve the real problem of butyl methoxydibenzoylmethane yellow-dyed clothing in daily life. In addition, some scientists prepare the glycyrrhizin and butyl methoxy dibenzoyl methane into the liposome by adopting a liposome method (CN 116650348A), and the method can improve the dispersibility, safety and stability of the butyl methoxy dibenzoyl methane, but the liposome is low in price, and the bonding force between the AVB and the liposome is weak, so that the liposome needs to be considered for long-term use.
Disclosure of Invention
The invention aims to provide a method for stabilizing butyl methoxy dibenzoyl methane serving as an organic sun-screening agent, which solves the problem that butyl methoxy dibenzoyl methane is unstable and simultaneously solves the problem that yellow clothes are easy to dye in practical application.
The method for stabilizing the organic sun-screening agent butyl methoxy dibenzoyl methane comprises the following steps:
A. zinc nitrate and TiCl 4 Dissolving urea in water, transferring into a hydrothermal reaction kettle, reacting at 100-130 ℃ for 47-50h, washing with water and ethanol, and vacuum drying to obtain hydrotalcite precursor;
B. placing the hydrotalcite precursor in a muffle furnace, and roasting for 2-3h at 200-400 ℃;
C. dispersing hydrotalcite containing oxygen vacancy obtained by roasting into a mixed solvent of distilled water and ethanol for removing carbon dioxide, adjusting the pH to 9-10 by using a pH regulator, stirring and reacting for 6-8 hours at 60-80 ℃ under the protection of nitrogen, washing with water and ethanol, and vacuum drying to obtain the butyl methoxy dibenzoylmethane and hydrotalcite composite material.
The zinc nitrate and TiCl 4 The molar ratio of (2) to (3) to (1).
The molar ratio of urea to zinc nitrate is 2-7:1.
The volume ratio of the distilled water for removing the carbon dioxide to the ethanol is 5-1:1.
The temperature rising speed of the roasting is more than 50 ℃/min.
The pH regulator is sodium hydroxide and sodium bicarbonate water solution.
The metal element on the hydrotalcite laminate in the composite material is coordinated with the beta-diketone structure in butyl methoxy dibenzoyl methane to form a stable six-membered ring structure.
According to the invention, more hydrotalcite oxygen vacancies are constructed by adjusting the roasting temperature and mode, then the butylmethoxydibenzoyl methane is loaded on the hydrotalcite by utilizing the reconstruction effect of the hydrotalcite, so that metal elements on a hydrotalcite laminate are coordinated with beta-diketone structures in the butylmethoxydibenzoyl methane to form a stable six-membered ring structure, the structure can obviously improve the photostability and chemical stability of the butylmethoxydibenzoyl methane by occupying a place in advance, the photodegradation rate is reduced from 15.06% to 4.06% under the same dose of ultraviolet irradiation, and other organic sunscreens are not required to be added, so that the efficacy is ensured, and meanwhile, the human body and environmental safety of finished cosmetics are improved. The mixed solvent of distilled water and ethanol is adopted, so that oxygen vacancies generated by roasting are better reserved, and the coordination of metal elements on the hydrotalcite laminate and beta-diketone structure in butyl methoxy dibenzoyl methane is facilitated to form a stable six-membered ring structure. The invention prepares the butyl methoxy dibenzoyl methane and hydrotalcite into the organic-inorganic composite ultraviolet resistant material, the butyl methoxy dibenzoyl methane and hydrotalcite have the advantages of obviously improving ultraviolet absorption through synergistic effect, along with good biocompatibility and long-term stability.
Drawings
FIG. 1 is an X-ray diffraction pattern (a: znTi-LDH; b: AVB; c: AVB@ZnTi-LDH) of the composite material prepared in example 1.
FIG. 2 is a solid ultraviolet absorbance spectrum of the AVB@ZnTi-LDH composite material and the physical mixture of AVB and ZnTi-LDH in example 2.
FIG. 3 is a graph showing changes in AVB concentration before and after irradiation with light, wherein the AVB@ZnTi-LDH composite material prepared in example 3 is prepared as a solution with an AVB concentration of 7mg/ml and as an AVB concentration of the same concentration.
FIG. 4 is a graph showing the color change of example 4 when AVB@ZnTi-LDH composite material and AVB were formulated into a solution of the same AVB concentration while adding the same amount of ferric ion solution.
FIG. 5 is a model of AVB@ZnTi-LDH composite material calculated by DFT (blue: ti; purple: zn; red: O; brown: C; white: H).
Detailed Description
Example 1:
1) Preparation of LDH precursor:
4.8g (0.08 mol) of Zn (NO) was precisely weighed 3 ) 2 ·6H 2 O、880μL(0.04mol)TiCl 4 And 6g (0.5 mol) of urea were dissolved in 200mL of water,and (3) fully and uniformly stirring the mixture at room temperature, placing the obtained suspension into a hydrothermal reaction kettle, reacting at 130 ℃ for 48 hours, washing with water and ethanol, and vacuum drying for 12 hours to obtain the hydrotalcite precursor.
2) LDH roasting and AVB@LDH composite material preparation:
placing hydrotalcite precursor in a muffle furnace, roasting for 2 hours at 200 ℃, taking 1g and 6g of butyl methoxy dibenzoyl methane from the roasted hydrotalcite, and dissolving the 1g and 6g of butyl methoxy dibenzoyl methane into 100ml of distilled water and ethanol with volume ratio of 1:1 for removing carbon dioxide; 2g of sodium hydroxide and 4.2g of sodium bicarbonate are weighed and dissolved in 100mL of distilled water to obtain a pH regulator, the mixed solution is regulated to 9 by using the pH regulator, and the mixed solution is vigorously stirred for 6 hours at 80 ℃ under the protection of nitrogen, washed by water and ethanol and dried in vacuum for 12 hours to obtain the composite material.
Characterization of the composite material prepared: as can be seen from fig. 1, the synthesized samples have both hydrotalcite and characteristic absorption peaks of butyl methoxydibenzoylmethane, indicating that butyl methoxydibenzoylmethane successfully binds to hydrotalcite.
Example 2:
1) Preparation of LDH precursor:
6g (0.1 mol) of Zn (NO) was precisely weighed 3 ) 2 ·6H 2 O、880μL(0.04mol)TiCl 4 And 6g (0.5 mol) of urea is dissolved in 200mL of water, the mixture is fully and uniformly stirred at room temperature, the obtained suspension is placed in a hydrothermal reaction kettle for reaction at 120 ℃ for 50 hours, and then water and ethanol are used for washing, and vacuum drying is carried out for 12 hours to obtain the hydrotalcite precursor.
2) LDH roasting and AVB@LDH composite material preparation:
placing hydrotalcite precursor in a muffle furnace, roasting for 3 hours at 200 ℃, taking 0.8g and 6g of butyl methoxy dibenzoylmethane from the roasted hydrotalcite, and dissolving the hydrotalcite precursor in 100ml of distilled water and ethanol with the volume ratio of 2:1 for removing carbon dioxide; 2g of sodium hydroxide and 4.2g of sodium bicarbonate are weighed and dissolved in 100mL of distilled water to obtain a pH regulator, the mixed solution is regulated to 10 by using the pH regulator, and the mixed solution is vigorously stirred for 6 hours at 80 ℃ under the protection of nitrogen, washed by water and ethanol and dried in vacuum for 12 hours to obtain the composite material.
As can be seen from fig. 2, the ultraviolet absorption of the composite material is obviously higher than that of the physical mixing of hydrotalcite and butyl methoxy dibenzoyl methane in equal proportion, which indicates that the composite material can achieve the synergistic effect of the hydrotalcite and butyl methoxy dibenzoyl methane.
Example 3:
1) Preparation of LDH precursor:
accurately weighing 7.2g (0.12 mmol) of Zn (NO) 3 ) 2 ·6H 2 O、880μL(0.04mol)TiCl 4 And 6g (0.5 mol) of urea is dissolved in 200mL of water, the mixture is fully and uniformly stirred at room temperature, the obtained suspension is placed in a hydrothermal reaction kettle for reaction at 130 ℃ for 48 hours, and then water and ethanol are used for washing, and vacuum drying is carried out for 12 hours to obtain the hydrotalcite precursor.
2) LDH roasting and AVB@LDH composite material preparation:
placing hydrotalcite precursor in a muffle furnace, roasting for 2 hours at 300 ℃, taking 0.6g and 6g of butyl methoxy dibenzoylmethane from the roasted hydrotalcite, and dissolving the hydrotalcite precursor in 100ml of distilled water and ethanol with the volume ratio of 3:1 for removing carbon dioxide; 2g of sodium hydroxide and 4.2g of sodium bicarbonate are weighed and dissolved in 100mL of distilled water to obtain a pH regulator, the mixed solution is regulated to 10 by using the pH regulator, and the mixed solution is vigorously stirred for 6 hours at 80 ℃ under the protection of nitrogen, washed by water and ethanol and dried in vacuum for 12 hours to obtain the composite material.
The photo stability of the samples was studied, and different samples were prepared as solutions having the same AVB concentration, and the AVB concentrations before and after uv irradiation were detected. As can be seen from fig. 3, the degradation rate of the composite material is reduced compared to butyl methoxydibenzoyl under uv irradiation, which is caused by the more stable six-membered ring structure formed by the β -diketone structure of butyl methoxydibenzoylmethane and hydrotalcite.
Example 4:
1) Preparation of LDH precursor:
accurately weighing 7.2g (0.12 mmol) of Zn (NO) 3 ) 2 ·6H 2 O、880μL(0.04mol)TiCl 4 And 6g (0.5 mol) of urea is dissolved in 200mL of water, the mixture is fully and uniformly stirred at room temperature, the obtained suspension is placed in a hydrothermal reaction kettle for reaction at 130 ℃ for 48 hours, and then water and ethanol are used for washing, and vacuum drying is carried out for 12 hours to obtain the hydrotalcite precursor.
2) LDH roasting and AVB@LDH composite material preparation:
placing hydrotalcite precursor in a muffle furnace, roasting for 3 hours at 300 ℃, taking 1g and 6g of butyl methoxy dibenzoyl methane from the roasted hydrotalcite, and dissolving the 1g and 6g of butyl methoxy dibenzoyl methane into 100ml of distilled water with the volume ratio of 4:1 for removing carbon dioxide and ethanol; 2g of sodium hydroxide and 4.2g of sodium bicarbonate are weighed and dissolved in 100mL of distilled water to obtain a pH regulator, the mixed solution is regulated to 9 by using the pH regulator, and the mixed solution is vigorously stirred for 6 hours at 80 ℃ under the protection of nitrogen, washed by water and ethanol and dried in vacuum for 12 hours to obtain the composite material.
The chemical stability of the sample was studied and butyl methoxydibenzoylmethane reacted with ferric ion to form a reddish brown material. Samples were prepared as solutions of the same AVB concentration, and equal amounts of iron ions were added to the solutions, respectively. As shown in fig. 4, the chemical stability of butyl methoxy dibenzoyl methane in the composite material is improved, because the beta-diketone structure of butyl methoxy dibenzoyl methane and hydrotalcite form a stable six-membered ring structure, the reaction with ferric ions is reduced, and the phenomenon that the ferric ions are easy to change color, which is plagued for a long time, is solved; FIG. 5 simulates the course of AVB@ZnTi-LDH synthesis by computational chemistry, when the beta-diketone structure of butyl methoxydibenzoylmethane coordinates with the exposed metal on hydrotalcite containing oxygen vacancies, forming a six membered ring, the course of the reaction being exothermic, indicating that this mode of binding is reasonable.
Claims (7)
1. A method for stabilizing butyl methoxy dibenzoylmethane as an organic sunscreen agent, which is characterized by comprising the following specific steps:
A. zinc nitrate and TiCl 4 Dissolving urea in water, transferring into a hydrothermal reaction kettle, reacting at 100-130 ℃ for 47-50h, washing with water and ethanol, and vacuum drying to obtain hydrotalcite precursor;
B. placing the hydrotalcite precursor in a muffle furnace, and roasting for 2-3h at 200-400 ℃;
C. dispersing hydrotalcite containing oxygen vacancy obtained by roasting into a mixed solvent of distilled water and ethanol for removing carbon dioxide, adjusting the pH to 9-10 by using a pH regulator, stirring and reacting for 6-8 hours at 60-80 ℃ under the protection of nitrogen, washing with water and ethanol, and vacuum drying to obtain the butyl methoxy dibenzoylmethane and hydrotalcite composite material.
2. The process of claim 1 wherein the zinc nitrate and TiCl 4 The molar ratio of (2) to (3) to (1).
3. The method according to claim 1, wherein the molar ratio of urea to zinc nitrate is 2-7:1.
4. The method of claim 1, wherein the volume ratio of distilled water to ethanol from which carbon dioxide is removed is 5-1:1.
5. The method of claim 1, wherein the firing is at a rate of greater than 50 ℃/min.
6. The method of claim 1, wherein the pH adjuster is an aqueous solution of sodium hydroxide and sodium bicarbonate.
7. The method of claim 1, wherein the metal element on the hydrotalcite laminate in the composite material coordinates with the β -diketone structure in butyl methoxydibenzoylmethane to form a stable six-membered ring structure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311762973.4A CN117731545A (en) | 2023-12-20 | 2023-12-20 | Method for stabilizing organic sun-screening agent butyl methoxy dibenzoyl methane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311762973.4A CN117731545A (en) | 2023-12-20 | 2023-12-20 | Method for stabilizing organic sun-screening agent butyl methoxy dibenzoyl methane |
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