CN111870547A - Montmorillonite-loaded nano ZnO composite uvioresistant agent and preparation method thereof - Google Patents
Montmorillonite-loaded nano ZnO composite uvioresistant agent and preparation method thereof Download PDFInfo
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- 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
- A61K8/26—Aluminium; Compounds thereof
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
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- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention relates to a montmorillonite-loaded nano ZnO composite uvioresistant agent and a preparation method thereof, wherein natural flaky mineral montmorillonite is used as a carrier mineral raw material, a room-temperature solid-phase synthesis method is adopted, and the No. 1 is that mixed materials are weighed and ground according to the mass ratio of zinc sulfate heptahydrate to the montmorillonite mineral raw material of 2-5: 1 to prepare a zinc sulfate heptahydrate-montmorillonite mixture; weighing and grinding the mixed material according to the molar ratio of zinc sulfate heptahydrate to sodium oxalate being 1-2: 1 to prepare a precursor zinc oxalate-montmorillonite mixture; 3, adopting a centrifugal washing device to centrifugally wash and remove impurities in the precursor zinc oxalate-montmorillonite mixture; 4, drying the materials by adopting a drying device at the drying temperature of 105 ℃ for 3-6 h; and 5, roasting the load-dried material by adopting a roasting device, wherein the heating rate is 10-15 ℃/min, the roasting temperature is 400-550 ℃, and the temperature is kept for 2-4 h, so that the montmorillonite-loaded nano ZnO composite uvioresistant agent is obtained. The method has the advantages of obvious effect, good safety, simple process, easy popularization and application, wide application and remarkable social and economic benefits.
Description
1. Field of the invention
The invention relates to a montmorillonite-loaded nano ZnO composite uvioresistant agent and a preparation method thereof.
2. Background of the invention
2.1 ultraviolet concept
Ultraviolet (UV) is an electromagnetic wave having a wavelength of 200nm to 400 nm. Ultraviolet rays in sunlight can be divided into three sections of long-wave ultraviolet ray UVA (320-400 nm), medium-wave ultraviolet ray UVB (280-320 nm) and short-wave ultraviolet ray UVC (200-280 nm) according to different wavelengths. Proper sunlight irradiation can increase oxygen content of body cells, reduce blood sugar and cholesterol content, and enhance human vitality. However, when the sun is excessively exposed for a long time, various skin diseases such as sunburn, freckle, acne and the like are easily induced and aggravated, and internal organs of the body are damaged in severe cases. The basic characteristics of the uv segments are now collated as shown in table 1.
TABLE 1 classification and characterization of UV
The short wave ultraviolet UVC is absorbed by the ozone layer, cannot reach the ground and has no effect on human bodies. The energy of the medium-wave ultraviolet UVB is highest, and the great part of the energy is absorbed by the skin dermis to cause the dermal blood vessels to expand and present the symptoms of red swelling, blisters and the like. If the skin is subjected to UVB irradiation for a long time, the skin can generate erythema, inflammation and skin aging, and skin cancer can be seriously caused. In daily life, 95% or more of ultraviolet rays which the skin comes into contact with are UVA, the penetration force is strong, the skin is photo-aged, skin cancer is caused, and UVA attracts people gradually in recent years.
Ultraviolet rays not only cause harm to human bodies, but also have certain damage and aging effects on coatings, plastics, printing ink and other high polymer materials, so that the high polymer materials have the phenomena of light loss, fading, yellowing, cracking, peeling, embrittlement, pulverization, strength reduction, delamination and the like. Even indoor light and sunlight transmitted through a glass window can degrade some materials.
Therefore, ultraviolet rays have considerable harm to human health, high polymer materials and the like, so that the research and application of the ultraviolet resistant agent or the ultraviolet shielding material have important practical significance.
2.2 research and State of the Art ultraviolet Shielding materials
Since the discovery of the hazards of ultraviolet light by humans, some means have been taken to shield ultraviolet light. Ultraviolet shielding materials for human skin protection are mainly of two types: one category is ultraviolet resistant textiles including sun protection clothing, sun protection hats, sun protection gloves, and sun protection umbrellas, among others. The ultraviolet resistant coating is a sunscreen skin care product or a cosmetic mainly used in daily life, and is prepared into a paste or liquid semi-liquid product by mutually matching ultraviolet resistant sunscreens (organic or inorganic) or compounding the ultraviolet resistant sunscreens with other components. The ultraviolet shielding material for protecting the high polymer material is mainly a filler with an ultraviolet shielding function, but the research on the aspect is relatively weak.
The anti-ultraviolet agent in skin care products or cosmetics means a substance which can effectively absorb or scatter solar radiation, can reduce damage to the skin, and can effectively absorb or scatter long-wave ultraviolet rays (UVA) and medium-wave ultraviolet rays (UVB) in sunlight. They can be divided into physical and chemical sunscreens by their protective mechanism of action, also commonly referred to as inorganic and organic sunscreens, respectively.
Chemical sunscreens (organic sunscreens), also known as uv absorbers, are primarily organic compounds which absorb harmful uv radiation. Among them, tert-butyl methoxydibenzoylmethane is the most representative UVA segment ultraviolet absorbent in the current sunscreen cosmetics, and isooctyl methoxycinnamate is the most widely used UVB segment ultraviolet absorbent in the current sunscreen cosmetics. However, organic sunscreens often require strict precautions with respect to heat resistance, stability, ultraviolet absorption range, toxicity, etc., which act only in a single wavelength band (UVA or UVB), and which may also decompose and lose the sunscreen effect under the action of light, with a short duration of action. In contrast, inorganic sunscreens (physical sunscreens) are more stable and safer, and they achieve the goal of sunscreening by primarily scattering ultraviolet light while absorbing ultraviolet light in small amounts. Inorganic sunscreens are increasingly widely used due to their advantages of high efficiency, safety, durability, etc.
Current inorganic sunscreens (physical sunscreens) are predominantly TiO2And ZnO, both of which are semiconductor materials, TiO2Mainly aiming at UVB protection, ZnO mainly shields UVA. But the sun-screening and ultraviolet screening effects of the two are closely related to the particle size or nanometer effect of the two. The results of the previous study show that when both are nanoparticles, i.e. TiO2When the particle size is 30-50 nm (grandma et al, 1998) and the particle size of ZnO is 10-35 nm, the nano effect is prominent, and the sunscreen ultraviolet shielding effect is excellent (YaoOer et al, 2003).
Nanometer ZnO is used as a widely used physical sun-screening agent, the principle of shielding ultraviolet rays is to absorb and scatter the ultraviolet rays, and the nanometer ZnO has the characteristics of small particle size, large specific surface area, good stability, small irritation and the like; in addition to good ultraviolet shielding performance, the antibacterial ultraviolet shielding material also has the advantages of safety, stability, heat resistance, certain antibacterial property and the like, so the antibacterial ultraviolet shielding material is widely applied to the field of sunscreen skin care products or cosmetics in recent years.
However, as the nano ZnO has the characteristics of weak polarity and tiny nano particles and high surface energy, the nano particles are in a thermodynamic unstable state and tend to agglomerate, thereby limiting the exertion of the nano effect and the ultraviolet shielding effect. In addition, in the process of manufacturing skin care products or cosmetics, nano ZnO particles are difficult to disperse to the original particle size, the ultraviolet absorption effect in the UVA, UVB, and UVC bands is reduced, the transparency and ultraviolet shielding performance thereof cannot be sufficiently exhibited, and the effect as a sunscreen agent in practical use is not good. In summary, as an inorganic sunscreen agent, the nano ZnO has the following main problems:
(1) agglomeration problem: the nano ZnO has high surface energy, and the particles tend to agglomerate.
(2) The problem of delamination: sunscreen product emulsionsThe density of the agent is about 0.96-1.1g/cm3And the density of the nano ZnO is about 5.6g/cm3Therefore, when the nano ZnO with high density is mixed into the emulsifier, the nano ZnO is easy to precipitate, and the delamination phenomenon is generated. The layering phenomenon greatly limits the use efficiency of the nano ZnO material, and the nano ZnO material cannot be directly mixed with common cosmetics for use. If the dispersion is used alone, the dispersion and the dispersion can be separated into layers, and the dispersion must be shaken well before being used. This not only causes inconvenience to the user but also increases the use cost.
(3) Health problems are as follows: the nanometer ZnO in the sunscreen product is easy to gather at the horny layer of the skin of a human body, the opening of hair follicle sebaceous glands and wrinkles, and the size of facial pores of the human body is generally 20 mu m, so the nanometer ZnO is easy to block the skin pores after long-term use, is not beneficial to the secretion of sweat and is easy to cause skin infection. Furthermore, trace amounts of zinc may also be absorbed through the skin into the blood, which is very detrimental to human health, especially in sunburn and skin-damaged patients.
(4) The aesthetic problem is that: due to the aggregation of the nano ZnO, the phenomenon of unnatural whitening can be generated when the nano ZnO is smeared on the skin, and the aesthetic effect is influenced.
(5) Environmental problems: zn2+The dissolution and the generation of active oxygen may have certain influence on the environment and the ecosystem and are not easy to recycle.
(6) The price problem is as follows: because the nano ZnO can not be directly mixed with common cosmetics for use, in order to overcome the layering phenomenon of dispersion liquid when the nano ZnO is used alone, a small-sized special container and a device are needed in actual use, the production and use cost of physical sun-proof products is greatly increased, the market condition of the products is generally higher, and the using amount of the products is limited.
2.3 Current State of the Art for the preparation of Nano ZnO
The preparation method of nano ZnO mainly comprises three types, namely a liquid phase method, a solid phase method and a gas phase method according to different states of raw materials and preparation processes. Among them, the gas phase method is not suitable for wide application due to the disadvantages of harsh reaction conditions, high production cost, low product purity, etc. At present, the liquid phase method and the solid phase method are mainly adopted for preparing the nano ZnO, and the main advantages and disadvantages are shown in the table 2.
TABLE 2 advantages and disadvantages of the main preparation method of nano ZnO
2.4 research technical status of mineral-loaded nano ZnO composite uvioresistant agent
The problems of nano ZnO agglomeration, delamination and the like are solved, and the method can be started from two aspects: firstly, a certain preparation method is adopted to modify nano ZnO, regulate and control the shape of the nano ZnO and the like; firstly, the mineral is used as a carrier to load nano ZnO. The leading research progress of the predecessors was as follows:
US 6086666 discloses a method for preparing a flaky mineral loaded nano ZnO anti-ultraviolet material by a hydrolysis precipitation method, which is characterized in that a zinc source and a precipitator are added into an aqueous solution of minerals at a certain reaction temperature for reaction, and after a certain time, the mixture is filtered, dried and calcined to obtain the anti-ultraviolet composite material, wherein the flaky material can be muscovite, sericite, talc and kaolinite.
CN 104017393a discloses a method for preparing nano ZnO-coated sericite powder composite material by room temperature solid phase synthesis, which is characterized in that in an aqueous solution system, calcium hydroxide or calcium oxide is added into a mixed system of sericite powder and zinc sulfate solution to directly obtain the nano ZnO-coated sericite powder composite material. The obtained composite material has good dispersibility in an organic solvent, and has excellent uvioresistant performance and antibacterial and deodorant performance.
Gongmeizhuo, Zhengshuilin, etc. (2017) mention that the hydrolytic precipitation method is adopted to coat nano ZnO on the surface of calcined kaolin to prepare the nano ZnO/calcined kaolin composite anti-ultraviolet powder material, and the composite powder material has good anti-ultraviolet performance under the proper preparation conditions, namely, the coating amount is 8%, the reaction temperature is 90 ℃, the modification time is 10min, the pulp concentration is 10:1, and the calcination temperature is 400 ℃.
From the above description, the preparation method adopted in the prior art for the mineral-supported nano ZnO is mainly a liquid phase method. According to the search of the inventor, no technical result report for preparing the montmorillonite-loaded nano ZnO composite uvioresistant agent by adopting a room-temperature solid-phase synthesis method exists at present.
3. Technical scheme
The invention aims to prepare a composite uvioresistant agent or an ultraviolet shielding material by taking natural flaky mineral montmorillonite with a layered structure as a raw material and loading nano ZnO, so as to overcome the problems of easy agglomeration, easy delamination, poor dispersibility and the like of the existing nano ZnO, improve the sun-screening and ultraviolet-shielding performances, improve the aesthetic effect, prevent the whitening phenomenon, improve the use efficiency and reduce the use cost. To achieve the above object, the following technical problems must be solved:
(1) selection of carrier mineral raw materials: the layered structure silicate minerals are of various types, and the selection conditions are as follows: has a layered structure and two-dimensional habit crystals, and mineral crystals are mainly in a fine scale shape, are non-toxic and harmless, and have rich mineral raw materials.
(2) Selecting a preparation method of nano ZnO: as shown in Table 2, several methods of the present invention have advantages and disadvantages, and the selection conditions of the preparation method of the present invention are: no toxicity and harm, convenience and feasibility and good effect.
(3) The preparation process of the room temperature solid phase synthesis method of nano ZnO comprises the following steps: on the basis of the work in the step (2), the process conditions for preparing the nano ZnO by the room-temperature solid-phase synthesis method are further determined by experiments.
(4) The preparation process of the montmorillonite-loaded nano ZnO composite uvioresistant agent comprises the following steps: on the basis of the work in the step (3), the process conditions for preparing the montmorillonite-loaded nano ZnO composite uvioresistant agent by adopting a room-temperature solid-phase synthesis method are further determined through experiments.
The specific technical scheme is as follows:
3.1 selection of Carrier mineral raw materials
Montmorillonite is 2:1 type dioctahedral layered structure water-rich aluminosilicate mineral, including calcium-based montmorillonite and sodium-based montmorillonite, and has crystal chemical formula of (Na, Ca)0.33(Al,Mg)2[Si4O10](OH)2·nH2O, theoretical chemical composition is Al2O315.97％，SiO253.98% and H2O22.18 percent; when cation Na is exchangeable between layers+、Ca2+When the contents of (A) are different, the names of the mineral species are also different, namely ENa +/ECa 2+<1 hour is calcium-based montmorillonite, and the characteristic peak d is identified by X-ray powder crystal diffraction analysis(001)In that
When E isNa +/ECa 2+Not less than 1, sodium-based montmorillonite, and d thereof(001)In that
Montmorillonite is monoclinic system, and its crystal structure is composed of two layers of SiO4]Tetrahedron and a layer of [ (Al, Mg) O6]The octahedron is formed, has a typical 2:1 layer structure, is very soft, smooth, non-toxic, harmless and stable in chemical property, and meets the requirements of serving as a nano ZnO carrier mineral.
FIG. 1 is an X-ray powder diffraction pattern (XRD) of a montmorillonite sample used in the present invention, and it can be seen that the pattern of the montmorillonite raw material is in accordance with the characteristic peaks of standard card PDF #13-0135 (montmorillonite) and PDF #39-1425 (cristobalite), and belongs to calcium-based montmorillonite. The intensity of the cristobalite peaks in the graph is relatively weak, indicating that the impurity phase cristobalite is relatively low in content and the purity of montmorillonite is high. The montmorillonite mineral material usually contains a small amount or a trace amount of quartz, feldspar, zeolite, and the like.
3.2 selection of preparation method of Nano ZnO
According to related documents, the invention adopts five methods shown in Table 2, prepares nano ZnO under optimized conditions, and further detects and analyzes the ultraviolet shielding performance of the nano ZnO by adopting an ultraviolet-visible light spectrophotometer, and the result is shown in figure 2.
According to the purpose and requirement of the invention, the ultraviolet resistant agent or the ultraviolet shielding material not only ensures higher absorbance of the ultraviolet region, but also ensures high transmittance of the visible region. As can be seen from fig. 2, the industrial ZnO has coarse particles and poor uv shielding performance, and thus is not satisfactory. The standard for distinguishing the ultraviolet resistance of domestic products at present is divided into the following parts according to the ultraviolet shielding rate: class a, the ultraviolet shielding rate is more than 90 percent; b level, ultraviolet shielding rate is 80-90%; c level, and the ultraviolet shielding rate is 50-80%. The ultraviolet resistant agent or ultraviolet shielding material should be selected from a class a as appropriate. As shown in figure 2, the ultraviolet shielding rate of the nano ZnO prepared by the room temperature solid phase synthesis method is more than 90 percent, belongs to a grade and meets the requirement of the invention.
Room temperature solid phase synthesis method preparation process of 3.3 nano ZnO
The invention further determines the technological conditions for preparing the nano ZnO by the room temperature solid phase synthesis method through experiments, and the technological conditions are as follows:
(1) preparing a precursor zinc oxalate: weighing zinc sulfate heptahydrate (ZnSO) according to the molar ratio of 1-2: 14·7H2O) and sodium oxalate (Na)2C2O4) And further grinding and mixing for 30-40 min to obtain a precursor zinc oxalate (ZnC)2O4·2H2O)；
(2) Washing to remove impurities: carrying out centrifugal washing on the precursor zinc oxalate by adopting a centrifugal washing device, washing with distilled water twice, and washing with absolute ethyl alcohol twice to remove impurities;
(3) drying the materials: transferring the washed and impurity-removed precursor zinc oxalate into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 3-6 h;
(4) roasting synthesis: heating the dried precursor zinc oxalate to 400-550 ℃ by adopting a roasting device in an air environment at the heating rate of 10-15 ℃/min, and preserving the heat for 2-4 h to obtain the nano ZnO.
FIG. 3 is the X-ray powder diffraction pattern of nano ZnO prepared by room temperature solid phase synthesis, and it can be seen that three standard strong peaks with sharp peak shape and high intensity appear in the range of 30-40 degree diffraction angle, namely
This is essentially coincident with the nano ZnO standard PDF card (36-1451). Considering that the characteristic peaks appearing in the whole angle diffraction range are relatively sharpThe results show that the nano ZnO sample has better crystal form and more complete crystallization. Meanwhile, no miscellaneous peak which can not correspond to the standard card appears in the diffraction map, which indicates that the purity of the sample is higher.
FIG. 4 is a scanning electron microscope analysis photo of nano ZnO prepared by room temperature solid phase synthesis, which shows that the nano ZnO powder crystal grain is spherical or quasi-spherical, has the characteristics of nano particles, the particle size is 30 nm-50 nm, but the agglomeration phenomenon is more obvious.
3.4 preparation process of montmorillonite-loaded nano ZnO composite uvioresistant agent
On the basis of the work, the process conditions for preparing the montmorillonite-loaded nano ZnO composite uvioresistant agent by adopting a room-temperature solid-phase synthesis method are further determined by experiments, and specifically comprise the following steps:
(1) preparation of a heptahydrate zinc sulfate-montmorillonite mixture: zinc sulfate heptahydrate (ZnSO)4·7H2O) and the montmorillonite mineral raw material in a mass ratio of 2-5: 1, respectively weighing a certain mass of zinc sulfate heptahydrate and montmorillonite mineral raw material powder, and further grinding and mixing for 30-40 min to obtain a zinc sulfate heptahydrate-montmorillonite mixture;
(2) preparation of precursor zinc oxalate-montmorillonite mixture: weighing a certain mass of sodium oxalate (Na) according to the molar ratio of zinc sulfate heptahydrate to sodium oxalate of 1-2: 12C2O4) Adding the mixture into a heptahydrate zinc sulfate-montmorillonite mixture, and continuously grinding for 50-60 min to obtain a precursor zinc oxalate (ZnC)2O4·2H2O) -montmorillonite mixtures;
(3) washing to remove impurities: adopting a centrifugal washing device to centrifugally wash the precursor zinc oxalate-montmorillonite mixture, washing with distilled water twice, washing with absolute ethyl alcohol twice, and removing impurities;
(4) drying the materials: transferring the washed and impurity-removed precursor zinc oxalate-montmorillonite mixture into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 3-6 h;
(5) roasting and loading: and heating the dried precursor zinc oxalate-montmorillonite mixture to 400-550 ℃ by adopting a roasting device at the heating rate of 10-15 ℃/min in an air environment, and preserving the heat for 2-4 h to obtain the montmorillonite-loaded nano ZnO composite anti-ultraviolet agent.
4. Technical advantages
(1) The effect is obvious. The montmorillonite is used as a carrier, a room temperature solid phase synthesis method is adopted to prepare the montmorillonite-loaded nano ZnO composite uvioresistant agent, and compared with nano ZnO prepared independently, the composite material has better uvioresistant performance or ultraviolet shielding performance, better dispersibility in a solvent and higher transmittance for visible light, and solves the problems of agglomeration, delamination, attractiveness and the like of the nano ZnO.
(2) The safety is good. The montmorillonite used in the invention is natural mineral, and is nontoxic and pollution-free. The raw material reagents used in the process of preparing the nano ZnO are nontoxic, safe and reliable.
(3) The process is simple. The room temperature solid phase synthesis method used in the invention has simple operation and convenient work.
(4) Easy popularization and application. The invention has simple process, convenient operation and easy learning, mastering, popularization and application.
(5) Has wide application and remarkable economic and social benefits. With the recognition of the harm of ultraviolet rays to human bodies, ultraviolet-resistant materials are receiving more and more attention, and especially, compared with chemical ultraviolet-resistant agents, physical ultraviolet-resistant agents are safer and more stable. The montmorillonite-loaded nano ZnO composite uvioresistant agent prepared by the invention better solves the technical problems of agglomeration of the current nano ZnO and the like, has important significance for the development of the uvioresistant material industry, and has wide application prospect and remarkable economic and social benefits.
5. Description of the drawings
FIG. 1: the X-ray powder crystal diffraction spectrum of the montmorillonite sample adopted by the invention.
FIG. 2: the ultraviolet shielding performance (Abs-absorbance and T-ultraviolet shielding rate) of the nano ZnO prepared by different methods.
FIG. 3: x-ray powder diffraction spectrum of nano ZnO prepared by room temperature solid phase synthesis.
FIG. 4: scanning electron microscope analysis photo of nano ZnO prepared by room temperature solid phase synthesis method.
FIG. 5: montmorillonite, nano ZnO and an X-ray powder crystal diffraction spectrum of the montmorillonite-loaded nano ZnO composite uvioresistant agent.
FIG. 6: scanning electron microscope analysis photos of the montmorillonite (a) and the montmorillonite-supported nano ZnO uvioresistant agent (b).
FIG. 7: montmorillonite, industrial ZnO, nano ZnO, and ultraviolet-visible light spectrum contrast chart (Abs-absorbance, T-ultraviolet shielding rate) of montmorillonite-loaded nano ZnO composite ultraviolet resistant agent.
6. Detailed description of the preferred embodiments
Example 1: montmorillonite-loaded nano ZnO composite uvioresistant agent and preparation method thereof
The preparation method is characterized in that natural flaky mineral montmorillonite is used as a carrier mineral raw material, the main mineral component of the montmorillonite mineral raw material is calcium-based montmorillonite (figure 1), montmorillonite crystals are irregular flaky, the flaky size is 0.5-3 mu m (figure 6a), a room-temperature solid-phase synthesis method is adopted to prepare the talc-loaded nano ZnO composite uvioresistant agent, and the preparation process comprises the following 5 steps:
(1) preparation of a heptahydrate zinc sulfate-montmorillonite mixture: zinc sulfate heptahydrate (ZnSO)4·7H2O) and the montmorillonite mineral raw material in a mass ratio of 2-5: 1, respectively weighing a certain mass of zinc sulfate heptahydrate and montmorillonite mineral raw material powder, and further grinding and mixing for 30-40 min to obtain a zinc sulfate heptahydrate-montmorillonite mixture;
(2) preparation of precursor zinc oxalate-montmorillonite mixture: weighing a certain mass of sodium oxalate (Na) according to the molar ratio of zinc sulfate heptahydrate to sodium oxalate of 1-2: 12C2O4) Adding the mixture into a heptahydrate zinc sulfate-montmorillonite mixture, and continuously grinding for 50-60 min to obtain a precursor zinc oxalate (ZnC)2O4·2H2O) -montmorillonite mixtures;
(3) washing to remove impurities: adopting a centrifugal washing device to centrifugally wash the precursor zinc oxalate-montmorillonite mixture, washing with distilled water twice, washing with absolute ethyl alcohol twice, and removing impurities;
(4) drying the materials: transferring the washed and impurity-removed precursor zinc oxalate-montmorillonite mixture into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 3-6 h;
(5) roasting and loading: and heating the dried precursor zinc oxalate-montmorillonite mixture to 400-550 ℃ by adopting a roasting device at the heating rate of 10-15 ℃/min in an air environment, and preserving the heat for 2-4 h to obtain the montmorillonite-loaded nano ZnO composite anti-ultraviolet agent.
The detection result shows that the montmorillonite-loaded nano ZnO composite uvioresistant agent obtained by the method of the embodiment has the following characteristics:
(1) fig. 5 is an X-ray powder diffraction pattern of montmorillonite, nano ZnO and montmorillonite-supported nano ZnO composite anti-uv agent, and it can be seen that the diffraction peak intensity of montmorillonite in the XRD pattern of montmorillonite-supported nano ZnO composite anti-uv agent is very weak compared to montmorillonite and nano ZnO, which shows that after calcination at 500 ℃, structural water in montmorillonite is partially removed and the crystal structure is destroyed. No new peak is generated, which indicates that the two systems are physically compounded.
(2) Fig. 6 is a Scanning Electron Microscope (SEM) photograph of the montmorillonite (a) and the montmorillonite-supported nano ZnO uvioresistant agent (b), and it can be seen that nano ZnO particles are supported on the surface of the montmorillonite flakes, the particle size distribution is uniform, the montmorillonite flakes are spherical, the size of the montmorillonite flakes is about 30nm to 50nm, and the agglomeration phenomenon is obviously improved.
(3) Fig. 7 is a graph comparing ultraviolet-visible light spectra of montmorillonite, industrial ZnO, nano ZnO, and montmorillonite-supported nano ZnO composite anti-ultraviolet agent, and it can be seen that: first, both montmorillonite and industrial ZnO have poor uv resistance and do not meet the performance requirements of uv resistance agents. Secondly, compared with industrial ZnO, the absorbance of the nano ZnO in an ultraviolet region is obviously increased, the ultraviolet resistance is excellent, the ultraviolet shielding rate can reach 95%, the transmittance in a visible light region is lower, and the whiteness is lower than that of the industrial ZnO. Thirdly, compared with nano ZnO, the montmorillonite-loaded nano ZnO uvioresistant agent has the advantages that the absorbance in an ultraviolet region is further improved, the ultraviolet shielding rate is close to 99%, the uvioresistant performance is excellent, the transmittance to visible light is better than that of the prepared nano ZnO, and the transparency is good.
The detection results show that the montmorillonite-loaded nano ZnO composite anti-ultraviolet agent obtained by the embodiment of the invention can overcome the technical problems of easy agglomeration of the existing nano ZnO and the like, obviously improves the performance of the anti-ultraviolet or ultraviolet shielding material of the nano ZnO, and has good market prospect and social and economic benefits.
Fund project: the work subsidies national science fund projects (41572038, 41972039) and scientific research projects (16TD0011) funded by the university and development hall in Sichuan.
Claims (1)
1. A montmorillonite loaded nano ZnO composite uvioresistant agent and a preparation method thereof, which uses natural sheet mineral montmorillonite as a carrier mineral raw material and adopts a room temperature solid phase synthesis method to prepare the montmorillonite loaded nano ZnO composite uvioresistant agent, and is characterized in that:
(1) preparation of a heptahydrate zinc sulfate-montmorillonite mixture: zinc sulfate heptahydrate (ZnSO)4·7H2O) and the montmorillonite mineral raw material in a mass ratio of 2-5: 1, respectively weighing a certain mass of zinc sulfate heptahydrate and montmorillonite mineral raw material powder, and further grinding and mixing for 30-40 min to obtain a zinc sulfate heptahydrate-montmorillonite mixture;
(2) preparation of precursor zinc oxalate-montmorillonite mixture: weighing a certain mass of sodium oxalate (Na) according to the molar ratio of zinc sulfate heptahydrate to sodium oxalate of 1-2: 12C2O4) Adding the mixture into a heptahydrate zinc sulfate-montmorillonite mixture, and continuously grinding for 50-60 min to obtain a precursor zinc oxalate (ZnC)2O4·2H2O) -montmorillonite mixtures;
(3) washing to remove impurities: adopting a centrifugal washing device to centrifugally wash the precursor zinc oxalate-montmorillonite mixture, washing with distilled water twice, washing with absolute ethyl alcohol twice, and removing impurities;
(4) drying the materials: transferring the washed and impurity-removed precursor zinc oxalate-montmorillonite mixture into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 3-6 h;
(5) roasting and loading: and heating the dried precursor zinc oxalate-montmorillonite mixture to 400-550 ℃ by adopting a roasting device at the heating rate of 10-15 ℃/min in an air environment, and preserving the heat for 2-4 h to obtain the montmorillonite-loaded nano ZnO composite anti-ultraviolet agent.
SaidMontmorillonite is 2:1 type dioctahedral layered structure water-rich aluminosilicate mineral, including calcium-based montmorillonite and sodium-based montmorillonite, and has crystal chemical formula of (Na, Ca)0.33(Al,Mg)2[Si4O10](OH)2·nH2O, wherein the X-ray powder diffraction analysis identification characteristic peaks of the calcium-based montmorillonite and the sodium-based montmorillonite are respectively
And
the montmorillonite mineral material contains small or trace amount of quartz, feldspar, zeolite, etc.
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