CN115282083B - Preparation method of lignin-based natural sun-proof compound - Google Patents
Preparation method of lignin-based natural sun-proof compoundInfo
- Publication number
- CN115282083B CN115282083B CN202210712843.9A CN202210712843A CN115282083B CN 115282083 B CN115282083 B CN 115282083B CN 202210712843 A CN202210712843 A CN 202210712843A CN 115282083 B CN115282083 B CN 115282083B
- Authority
- CN
- China
- Prior art keywords
- lignin
- solution
- sun
- silicon dioxide
- based natural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Cosmetics (AREA)
Abstract
本发明提供了一种木质素基天然防晒复合物的制备方法，具体包括以下步骤：首先采用水玻璃作为硅源以钛酸四丁酯作为钛源采用原位修饰的方法制备获得氨基修饰的复合二氧化硅/二氧化钛溶胶；其次，将氨基修饰的复合二氧化硅/二氧化钛溶胶与木质素反应制备获得二氧化硅/二氧化钛/木质素防晒复合物；二氧化硅、二氧化钛、木质素三者复配，成分相互叠加，共同发挥效能，使防晒范围更广，更有效地阻隔全波段的紫外线，达到良好的防晒效果。
The invention provides a method for preparing a lignin-based natural sunscreen composite, which specifically comprises the following steps: firstly, using water glass as a silicon source and tetrabutyl titanate as a titanium source, and adopting an in-situ modification method to prepare an amino-modified composite silica/titania sol; secondly, reacting the amino-modified composite silica/titania sol with lignin to prepare a silica/titania/lignin sunscreen composite; and the silica, titania and lignin are compounded, and the components are superimposed on each other to jointly exert their efficacy, thereby extending the sunscreen range, more effectively blocking ultraviolet rays of the entire wavelength range, and achieving a good sunscreen effect.
Description
Technical Field
The invention belongs to the technical field of sun-proof product processing, and particularly relates to a preparation method of a lignin-based natural sun-proof compound.
Background
Lignin is one of the three major components forming the plant skeleton, which is widely present in plant tissues. The annual global lignin production is close to 5000 ten thousand tons, mainly from the traditional pulp and paper industry and biomass refining residues. This amount may continue to increase in the future as lignin biomass is a sustainable alternative to petroleum to produce renewable fuels and chemicals. However, at present, more than 95% of industrial lignin is used as fuel, and is less than 5% of industrial utilization. The lignin after combustion is directly discharged into the environment, which is not only a resource waste, but also produces a certain pollution to the environment, which is contrary to the national development concept. Therefore, development and utilization of lignin are needed to make effective and reasonable use.
Lignin is a complex organic polymer, and has functional groups such as aromatic groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, carbonyl groups, methoxy groups and the like in a molecular structure, so that various chemical reactions can be carried out, and the lignin is endowed with certain ultraviolet absorption, antibacterial, antioxidant and other performances. Meanwhile, lignin has the characteristics of nature, no toxicity, reproducibility, biodegradability and the like, and has great utilization value. At present, lignin can be used for preparing fertilizers, additives, adhesives and the like after being improved, and has certain application in the fields of medicine, metallurgy, metal industry, printing and dyeing industry, building and the like, but the overall utilization rate is still low, and more lignin products with high added value need to be developed.
Today, more and more people begin to pay attention to sun protection, and it is becoming a more common practice to use sun protection products. The sun protection not only can prevent sunburn and sun black, but also can resist oxidation and aging. The sun-screening product can block ultraviolet rays and weaken the damage of the ultraviolet rays to the skin, thereby slowing down skin aging. The sun-screening products on the market are mainly divided into physical sun-screening and chemical sun-screening, wherein most of the sun-screening products are chemical sun-screening, and the sun-screening products are easy to irritate skin and can generate certain side effects on the skin. Therefore, the lignin is used as a natural ultraviolet blocking agent to prepare the sun-proof coating, and the comprehensive utilization rate of the lignin is expected to be further improved.
Lignin has the characteristics of scavenging free radicals, absorbing ultraviolet rays, resisting bacteria, resisting oxidation and the like, is regarded as a natural antioxidant, can be used as a natural ultraviolet blocking agent to prepare a sun-screening coating, can improve the additional utilization value of lignin, but has a darker color, limits the application range, has an unsatisfactory ultraviolet ray absorption effect as a plant sun-screening agent, and has good ultraviolet ray absorption, scattering and reflection capability. However, the agglomeration phenomenon of nano particles exists in the preparation process of nano TiO 2 particles, so that the physical barrier property of nano TiO 2 to ultraviolet rays is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a lignin-based natural sun-screening compound, which specifically comprises the following steps:
(1) Preparation of composite silica/titania sol:
1.1 Adding acid into the water glass to adjust the pH of the system to 8-9 to obtain a silicon dioxide precursor solution;
1.2 Dispersing tetrabutyl titanate in absolute ethyl alcohol to obtain a dispersion liquid, dropwise adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1) for stirring reaction, dropwise adding an aminosilane coupling agent into the mixture, and stirring reaction to obtain composite silicon dioxide/titanium dioxide sol;
(2) Placing the enzymatic hydrolysis lignin in a sodium hydroxide solution, adding glyoxal, adding composite silicon dioxide/titanium dioxide sol into the solution under the stirring condition, stirring the solution at 60 ℃ for reaction for 6-8 hours, filtering, washing and drying to obtain the lignin-based natural sun-proof compound;
the water glass in the step 1.1) is silicate water solution with the modulus of 2.0, the concentration of the silicate water solution is calculated by silicon dioxide, the mass concentration of silicon dioxide in the silicate water solution is 5%, and the silicate is one or two of sodium silicate and potassium silicate;
The molar ratio of the tetrabutyl titanate to the silicon dioxide in the water glass solution to the amino in the amino silane coupling agent is 5:1:3;
The aminosilane coupling agent is aminopropyl triethoxysilane and diammine propyl triethoxysilane;
The mass ratio of the enzymolysis lignin to the silicon dioxide in the water glass solution is 0.8-1.2:1;
The mass ratio of the enzymatic hydrolysis lignin to glyoxal is 10:1;
the drying in the step (2) is spray drying;
the invention also aims to provide the lignin-based natural sun-proof compound prepared by the method;
the lignin-based natural sun-screening compound is applied to sun-screening products.
The preparation method adopts water glass as a silicon dioxide source, and enables the water glass to be subjected to preliminary hydrolysis by adjusting the pH value to obtain a silicon dioxide precursor solution, tetrabutyl titanate is added into the silicon dioxide precursor solution to be subjected to hydrolysis to form silicon dioxide/titanium dioxide precursors, the precursors are subjected to polycondensation at a certain temperature to form nano silicon dioxide/nano titanium dioxide composite nano particles, the surfaces of the composite nano particles are provided with reactive groups of amino groups, the nano titanium dioxide and the nano silicon dioxide are mutually inserted, the stability of the nano particles is improved, secondary agglomeration is avoided, the specific surface area of the nano particles is effectively improved, complex instruments or reagents are not needed, the operation is simple and convenient, and the physical barrier performance of nano TiO 2 to ultraviolet rays can be remarkably improved.
The composite nanoparticle sol reacts with lignin and glyoxal at a certain temperature, and the composite nanoparticle is subjected to bonding reaction with lignin through amino groups, hydroxyl groups and other groups on the surface, so that the bonding strength and compatibility of the nanoparticle and the lignin are improved, meanwhile, the existence of the lignin obviously reduces the secondary agglomeration of the nanoparticle in the forming process, improves the dispersibility of the nanoparticle, further avoids the agglomeration of the nanoparticle, and improves the sun-screening performance.
Advantageous effects
The invention adopts an in-situ compounding mode to prepare the nano titanium dioxide/nano silicon dioxide/lignin compound, and the three components have synergistic effect and endow stronger light stability, so that the sun-proof coating with full-band ultraviolet blocking function is prepared. In addition, the lignin-based natural sun-proof compound has more excellent ultraviolet absorption effect than a pure mixture of nano titanium dioxide, nano silicon dioxide and lignin, and can effectively reduce the transmittance of ultraviolet rays.
The lignin-based natural sun-proof compound disclosed by the invention has the advantages that the nano titanium dioxide, the nano silicon dioxide and the lignin are subjected to chemical bonding, the dispersibility and the stability of the lignin-based natural sun-proof compound in a sun-proof coating are improved, the white nano titanium dioxide and the white nano silicon dioxide also neutralize the color of the lignin, the limitation that the color is dark and difficult to blend is broken, the dressing effect is better, the application range is wider, meanwhile, the three components are compounded, the components are mutually overlapped to jointly exert the efficacy, the sun-proof range is wider, the ultraviolet rays in all wave bands are blocked more effectively, and the good sun-proof effect is achieved.
The lignin-based natural sun-screening compound disclosed by the invention is used for preparing sun-screening products, so that the additional utilization value of lignin is improved, and the lignin-based natural sun-screening compound has very important significance for improving the comprehensive utilization level of lignin.
Drawings
FIG. 1 is a graphical representation of the mixture of commercial silk tower-fu emulsion and lignin-based sunscreen compounds prepared in examples 1-3 of the present invention at 30℃for 15 minutes.
FIG. 2 is a graph showing the change in UV transmittance of a lignin-based sunscreen composite and commercial silk dove emulsion hybrid sunscreen coating prepared in example 2 of the present invention and two commercial sunscreens;
The lignin-based sun-proof compound prepared in the embodiment 2 of the invention and the commercial silk tower Fu emulsion are mixed to form a sun-proof coating, b, the dream make-up is transparent and white sun-proof cream, c, the magnolia oil is multi-effect sun-proof cream.
Detailed Description
The technical scheme of the invention is described in detail below with reference to specific examples, and raw materials used in the invention are commercially available unless otherwise specified.
Example 1
The preparation method of the lignin-based natural sun-proof compound specifically comprises the following steps:
(1) Preparation of composite silica/titania sol:
1.1 300g of sodium silicate solution (the concentration is 5% of the mass concentration of the silicon dioxide, the modulus is 2), and sulfuric acid is added into the solution to adjust the pH of the system to 8-9, so as to obtain a silicon dioxide precursor solution;
1.2 Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid, gradually adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1), stirring uniformly, then dropwise adding an ethanol solution of aminopropyl triethoxysilane into the dispersion liquid, stirring and reacting for 3 hours to obtain a composite silicon dioxide/titanium dioxide sol, wherein the ethanol solution of aminopropyl triethoxysilane is obtained by dispersing 0.75mol of aminopropyl triethoxysilane into absolute ethyl alcohol with equal weight, and stirring uniformly;
(2) Placing 18.75g of enzymolysis lignin in a sodium hydroxide solution, adding 1.875g of glyoxal, adding the composite silica/titanium dioxide sol obtained in the step (1) into the solution under stirring, reacting for 6-8h at 60 ℃, filtering, washing, and spray-drying to obtain the lignin-based natural sun-proof compound.
Example 2
(1) Preparation of composite silica/titania sol:
1.1 300g of sodium silicate solution (the concentration is 5% of the mass concentration of the silicon dioxide, the modulus is 2), and sulfuric acid is added into the solution to adjust the pH of the system to 8-9, so as to obtain a silicon dioxide precursor solution;
1.2 Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid, gradually adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1), stirring uniformly, then dropwise adding an ethanol solution of aminopropyl triethoxysilane into the dispersion liquid, stirring and reacting for 3 hours to obtain a composite silicon dioxide/titanium dioxide sol, wherein the ethanol solution of aminopropyl triethoxysilane is obtained by dispersing 0.75mol of aminopropyl triethoxysilane into absolute ethyl alcohol with equal weight, and stirring uniformly;
(2) Placing 15g of enzymolysis lignin in a sodium hydroxide solution, adding 1.5g of glyoxal into the solution, adding the composite silica/titanium dioxide sol obtained in the step (1) into the solution under stirring, reacting the solution for 6 to 8 hours at 60 ℃, filtering the solution, washing the solution, and performing spray drying to obtain the lignin-based natural sun-proof compound.
Example 3
(1) Preparation of composite silica/titania sol:
1.1 300g of sodium silicate solution (the concentration is 5% of the mass concentration of the silicon dioxide, the modulus is 2), and sulfuric acid is added into the solution to adjust the pH of the system to 8-9, so as to obtain a silicon dioxide precursor solution;
1.2 Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid, gradually adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1), stirring uniformly, then dropwise adding an ethanol solution of aminopropyl triethoxysilane into the dispersion liquid, stirring and reacting for 3 hours to obtain a composite silicon dioxide/titanium dioxide sol, wherein the ethanol solution of aminopropyl triethoxysilane is obtained by dispersing 0.75mol of aminopropyl triethoxysilane into absolute ethyl alcohol with equal weight, and stirring uniformly;
(2) Placing 12.5g of enzymolysis lignin in a sodium hydroxide solution, adding 1.25g of glyoxal, adding the composite silica/titanium dioxide sol obtained in the step (1) into the solution under stirring, reacting for 6-8h at 60 ℃, filtering, washing, and spray-drying to obtain the lignin-based natural sun-proof compound.
Comparative example 1
The preparation method of the lignin-based natural sun-proof compound specifically comprises the following steps:
(1) Preparation of composite silica/titania nanoparticles:
1.1 300g of sodium silicate solution (the concentration is 5% of the mass concentration of the silicon dioxide, the modulus is 2), and sulfuric acid is added into the solution to adjust the pH of the system to 8-9, so as to obtain a silicon dioxide precursor solution;
1.2 Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid, gradually adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1), stirring uniformly, then dropwise adding an ethanol solution of aminopropyl triethoxysilane into the dispersion liquid, stirring at 60 ℃ for reacting for 5 hours, filtering and washing until no sulfate radical is contained in the washing liquid, and spray drying to obtain composite silicon dioxide/titanium dioxide nano particle powder, wherein the ethanol solution of aminopropyl triethoxysilane is obtained by dispersing 0.75mol of aminopropyl triethoxysilane into absolute ethyl alcohol with equal weight to uniformly stir;
(2) Placing 15g of enzymolysis lignin in a sodium hydroxide solution, adding 1.5g of glyoxal into the solution, adding the composite silica/titanium dioxide nano particles in the step (1) into the solution under stirring, reacting for 6-8h at 60 ℃, filtering, washing, and spray-drying to obtain the lignin-based natural sun-proof compound.
Comparative example 2
The preparation method of the lignin-based natural sun-proof compound specifically comprises the following steps:
(1) Preparation of composite silica/titania sol:
1.1 300g of sodium silicate solution (the concentration is 5% of the mass concentration of the silicon dioxide, the modulus is 2), and sulfuric acid is added into the solution to adjust the pH of the system to 8-9, so as to obtain a silicon dioxide precursor solution;
1.2 Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid, gradually adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1), uniformly stirring, and continuing stirring for reacting for 3 hours to obtain the composite silicon dioxide/titanium dioxide sol;
(2) Placing 15g of enzymolysis lignin in a sodium hydroxide solution, adding 1.5g of glyoxal into the solution, adding the composite silica/titanium dioxide sol obtained in the step (1) into the solution under stirring, reacting the solution for 6 to 8 hours at 60 ℃, filtering the solution, washing the solution, and performing spray drying to obtain the lignin-based natural sun-proof compound.
Comparative example 3
The preparation method of the lignin-based natural sun-proof compound specifically comprises the following steps:
(1) Dispersing 1.25mol of tetrabutyl titanate in absolute ethyl alcohol with equal mass to obtain a dispersion liquid;
(2) Placing 15g of enzymolysis lignin in a sodium hydroxide solution, adding 1.5g of glyoxal into the solution, adding tetrabutyl titanate dispersion liquid in the step (1) into the solution under stirring, reacting for 6-8h at 60 ℃, filtering, washing, and spray-drying to obtain the lignin-based natural sun-proof compound.
The lignin-based natural sun-proof composite prepared by the invention has the following characteristics:
Dispersing the lignin-based sunscreen compound prepared in the examples 1-3 and the comparative examples 1-3 in commercially available commercial emulsion silk tower, and stirring and mixing for 15min at 30 ℃ to obtain a sunscreen coating, wherein a physical diagram of the lignin-based sunscreen compound sunscreen coating prepared in the example is shown in figure 1;
The lignin-based sunscreen composite sun-screening coatings prepared in examples 1-3 and comparative examples 1-3 of the present invention were used as test groups, the UV transmittance was measured, commercial silk-tafu emulsion was used as reference group, and the test results are shown in Table 1.
TABLE 1
| UV transmittance (%) | |
| Example 1 | 16.18 |
| Example 2 | 15.66 |
| Example 3 | 16.75 |
| Comparative example 1 | 21.97 |
| Comparative example 2 | 25.59 |
| Comparative example 3 | 29.78 |
As can be seen from the data in table 1, the lignin-based sunscreen compounds prepared in examples 1-3 according to the present invention have lower transmittance to ultraviolet rays as a sunscreen coating, which indicates that the sunscreen compound coating of the present invention has excellent ultraviolet resistance.
Compared with example 2, the ultraviolet transmittance of the composite coating in comparative examples 1-3 is higher than that of the composite coating in example 2, the composite sun-proof coating in comparative example 1 is prepared by mixing composite nanoparticle powder with lignin to obtain sun-proof composite, the secondary agglomeration of nanoparticles in the preparation process of the composite nanoparticles reduces the contact probability of nano silicon dioxide and nano titanium dioxide with ultraviolet rays to reduce the absorptivity of ultraviolet rays, the aminosilane coupling agent is not added in the preparation process of the composite sol in comparative example 2, on one hand, the agglomeration of the composite nanoparticles is increased, on the other hand, the surface of the composite nanoparticles does not contain reactive groups amino, the reactivity is reduced in the process of compounding with lignin, the compatibility of the nanoparticles with lignin is poor, the stability of the sun-proof composite coating is poor, the nano titanium dioxide particles and lignin are compounded to obtain sun-proof composite, the sun-proof composite does not contain nano silicon dioxide in the preparation process of the sun-proof composite, the sun-proof coating has the increased ultraviolet transmittance, therefore, the in-proof composite method is adopted to prepare silicon dioxide/nano titanium dioxide precursor (composite silicon dioxide/titanium dioxide/lignin sol) firstly, and then the composite lignin is better in-situ dispersed to obtain the better in-situ dispersion effect of the composite lignin to obtain the composite lignin, and the better in-situ dispersion effect of the composite lignin can be better than that the lignin can be better than the natural lignin can absorb the ultraviolet particles in the composite particle.
Meanwhile, the UV transmittance of the lignin-based sunscreen composite sun-screening coating prepared in the embodiment 2 of the invention and the UV transmittance of two commercial sun-screening creams are tested in vitro, and the transmittance change curve is shown in figure 2;
As can be seen from FIG. 2, in the range of the wavelength of 400-10 nm, 98.7% of the ultraviolet rays reaching the earth surface are UVA (ultraviolet A, 400-320 nm), the ultraviolet transmittance of the commercially available dream make-up transparent and clear sun-protecting cream (curve b) and the magnolia oil multi-effect sun-protecting cream (curve c) is far higher than that of the lignin-based sun-protecting compound prepared in the embodiment 2 of the invention, and the ultraviolet transmittance of the commercially available magnolia oil multi-effect sun-protecting cream in the whole range of the wavelength fluctuates greatly and the stability is poor, so that the lignin-based sun-protecting compound prepared in the embodiment 2 of the invention has better sun-protecting effect than that of two commercial sun-protecting creams and shows good effect of blocking ultraviolet rays in the whole range.
The above embodiments are merely preferred embodiments of the present invention, the protection scope of the present invention is not limited thereto, and any simple changes or equivalent alternatives of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed herein fall within the protection scope of the present invention.
Claims (9)
1. The preparation method of the lignin-based natural sun-screening compound is characterized by comprising the following steps of:
(1) Preparation of composite silica/titania sol:
1.1 Adding acid into the water glass to adjust the pH of the system to 8-9 to obtain a silicon dioxide precursor solution;
1.2 Dispersing tetrabutyl titanate in absolute ethyl alcohol to obtain a dispersion liquid, dropwise adding the dispersion liquid into the silicon dioxide precursor solution in the step 1.1) for stirring reaction, dropwise adding an aminosilane coupling agent into the mixture, and stirring reaction to obtain composite silicon dioxide/titanium dioxide sol;
(2) Placing the enzymatic hydrolysis lignin in a sodium hydroxide solution, adding glyoxal, adding composite silicon dioxide/titanium dioxide sol into the solution under the stirring condition, stirring the solution at 60 ℃ for reaction for 6-8 hours, filtering, washing and drying to obtain the lignin-based natural sun-proof compound;
The molar ratio of the tetrabutyl titanate to the silicon dioxide in the water glass solution to the amino in the amino silane coupling agent is 5:1:3.
2. The method for preparing the lignin-based natural sunscreen compound according to claim 1 wherein the water glass in step 1.1) is an aqueous silicate solution having a modulus of 2.0, wherein the aqueous silicate solution has a concentration of 5% by mass of silica based on silica.
3. The method of making a lignin-based natural sunscreen composition according to claim 2 wherein the silicate is one or both of sodium silicate and potassium silicate.
4. The method for preparing lignin-based natural sun protection composite according to claim 1, wherein the aminosilane coupling agent is aminopropyl triethoxysilane, bis-aminopropyl triethoxysilane.
5. The method for preparing the lignin-based natural sun-screening compound according to claim 1, wherein the mass ratio of the enzymatic hydrolysis lignin to the silicon dioxide in the water glass solution is 0.8-1.2:1.
6. The method for preparing the lignin-based natural sun-screening compound according to claim 1, wherein the mass ratio of the enzymatic hydrolysis lignin to glyoxal is 10:1.
7. A method of preparing a lignin-based natural sunscreen composition according to claim 1 wherein the drying in step (2) is spray drying.
8. A lignin-based natural sunscreen compound prepared by the method of any one of claims 1-7.
9. Use of the lignin-based sunscreen compound according to claim 8 in a sunscreen product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210712843.9A CN115282083B (en) | 2022-06-22 | 2022-06-22 | Preparation method of lignin-based natural sun-proof compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210712843.9A CN115282083B (en) | 2022-06-22 | 2022-06-22 | Preparation method of lignin-based natural sun-proof compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115282083A CN115282083A (en) | 2022-11-04 |
| CN115282083B true CN115282083B (en) | 2025-07-29 |
Family
ID=83821023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210712843.9A Active CN115282083B (en) | 2022-06-22 | 2022-06-22 | Preparation method of lignin-based natural sun-proof compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115282083B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520386A (en) * | 2012-08-06 | 2015-04-15 | 禾大国际股份公开有限公司 | Particulate metal oxide particles comprising a metal oxide core and a coating layer comprising an inorganic material, a silane coupling agent and/or a hydrophobizing agent |
| CN113101235A (en) * | 2021-03-17 | 2021-07-13 | 华南理工大学 | In-situ titanium dioxide coated lignin composite particle and preparation and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312233C (en) * | 1999-01-11 | 2007-04-25 | 昭和电工株式会社 | Comsmetic preparation, surface-hydrophobized silica-coated metal oxide particles, sol of silica-coated metal oxide, and processes for producing these |
| GB0705614D0 (en) * | 2007-03-23 | 2007-05-02 | Croda Int Plc | Particulate titanium dioxide |
| US8481678B2 (en) * | 2009-03-30 | 2013-07-09 | E I Du Pont De Nemours And Company | Peptide-based tooth whitening reagents |
| KR101756697B1 (en) * | 2010-10-15 | 2017-07-13 | (주)아모레퍼시픽 | Solid cosmetic composition of oil in water for blocking ultraviolet rays |
| WO2019238261A1 (en) * | 2018-06-15 | 2019-12-19 | Ramirez Rios Liliana Patricia | METAL COMPLEXES OF β-DIKETONES AND/OR POLYPHENOLS BY GREEN CHEMISTRY, PREPARATION METHOD THEREOF, SUNSCREEN THEREOF, SKIN OR HAIR TONE CONCEALER THEREOF, HAIR DYEING THEREOF AND OTHER USES THEREOF |
| CN112972275B (en) * | 2021-04-13 | 2022-10-11 | 苏州绿叶日用品有限公司 | SiO with sun-proof performance 2 -TiO 2 Composite nano material and preparation method and application thereof |
-
2022
- 2022-06-22 CN CN202210712843.9A patent/CN115282083B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520386A (en) * | 2012-08-06 | 2015-04-15 | 禾大国际股份公开有限公司 | Particulate metal oxide particles comprising a metal oxide core and a coating layer comprising an inorganic material, a silane coupling agent and/or a hydrophobizing agent |
| CN113101235A (en) * | 2021-03-17 | 2021-07-13 | 华南理工大学 | In-situ titanium dioxide coated lignin composite particle and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Facile and Green Preparation of High UV-Blocking Lignin/Titanium Dioxide Nanocomposites for Developing Natural Sunscreens";Jue Yu等;《Industrial & Engineering Chemistry Research》;20181026;第15740-15748页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115282083A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106633967B (en) | A kind of titanium dioxide/lignin-base composite nanometer particle and preparation method and application | |
| CN105968852B (en) | The lignin-base zinc oxide composite particles and preparation method and application of anti-ultraviolet radiation | |
| JP5072820B2 (en) | Silicone resin composition | |
| CN101543466B (en) | Nano zinc oxide surface modifying method | |
| CN103436111A (en) | Preparation method of water-based ultraviolet barrier coating based on ZnO quantum dots | |
| WO2007097284A1 (en) | Uniformly dispersed photocatalyst coating liquid, method for producing same, and photocatalytically active composite material obtained by using same | |
| CN109607555B (en) | A kind of high friction high transparent toothpaste silica and preparation method thereof | |
| CN1807750A (en) | Method for in-situ generating inorganic nanoparticles in textile | |
| KR102176830B1 (en) | Silicon-oxide-coated zinc oxide and method for manufacturing same, silicon-oxide-coated zinc-oxide-containing composition, and cosmetic | |
| CN115110340B (en) | A multifunctional protective solution for paper | |
| CN1884095A (en) | UV-shielding nano normal zinc titanate powder and process for preparing same | |
| Yuan et al. | A UV-shielding and hydrophobic graphitic carbon nitride nanosheets/cellulose nanofibril (gCNNS/CNF) transparent coating on wood surface for weathering resistance | |
| Meng et al. | Transparent poly (methyl methacrylate)/TiO2 nanocomposites for UV-shielding applications | |
| CN112080021A (en) | A kind of preparation method of nanocellulose-induced titanium dioxide composite ultraviolet shielding material | |
| CN117820557A (en) | Ultraviolet-resistant ABS material, preparation method thereof and packaging bottle | |
| CN115282083B (en) | Preparation method of lignin-based natural sun-proof compound | |
| KR20000048167A (en) | Cationic resin modified silica dispersing solution and the method for preparing the same | |
| CN110564182A (en) | surface treatment process of special titanium dioxide for high weather-resistant paint | |
| CN117512994A (en) | A dodecanol-modified SiO2 nanoparticle superhydrophobic cotton fiber material | |
| JP4210785B2 (en) | Method for producing transparent coating agent for optical element containing rutile type titanium oxide sol | |
| CN111110575B (en) | Preparation method of physical sun-screening agent for cosmetics | |
| CN110980747B (en) | Low-viscosity high-transparency friction type silicon dioxide for toothpaste and preparation method thereof | |
| CN119060589A (en) | A method for preparing a water-based high-reflective heat-insulating coating | |
| EP4190971A1 (en) | Titanium dioxide pigment particles covalently bonded with a functionalized nanocellulose | |
| CN101748649B (en) | A kind of manufacture method of fly ash fiber pulp performance modifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |