CN111067813A - Kaolinite loaded nano TiO2Composite uvioresistant agent and its prepn process - Google Patents

Kaolinite loaded nano TiO2Composite uvioresistant agent and its prepn process Download PDF

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CN111067813A
CN111067813A CN201911322908.3A CN201911322908A CN111067813A CN 111067813 A CN111067813 A CN 111067813A CN 201911322908 A CN201911322908 A CN 201911322908A CN 111067813 A CN111067813 A CN 111067813A
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kaolinite
titanium sulfate
tio
urea
ultraviolet
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汪灵
梁唯丛
董秋冶
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Chengdu Univeristy of Technology
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    • 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
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • 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
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Abstract

The invention relates to kaolinite loaded nano TiO2A composite uvioresistant agent and a preparation technology thereof, wherein natural flaky mineral kaolinite is used as a carrier mineral raw material, a hydrothermal method is adopted, and step 1, a titanium sulfate solution of 0.3-1.2 mol/l is prepared and is uniformly stirred; 2, weighing urea according to the molar ratio of 1-3: 1 of urea to titanium sulfate, adding the urea to a titanium sulfate solution, uniformly mixing and stirring, and adding a proper amount of kaolinite to ensure that TiO in a mixed system is TiO2And the mass of kaoliniteThe weight ratio is 0.5-2, and the titanium sulfate-urea-kaolinite mixed solution is obtained after uniform stirring; performing hydrothermal reaction, pouring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting at the temperature of 140-200 ℃ for 2-8 h; 4, removing impurities in the mixed liquid by centrifugal washing; drying the material at 105 ℃ for 4-6 h to obtain the kaolinite loaded nano TiO2And (3) a composite anti-ultraviolet agent. 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

Kaolinite loaded nano TiO2Composite uvioresistant agent and its prepn process
1. Field of the invention
The invention relates toKaolinite loaded nano TiO2Composite uvioresistant agent and its prepn process, hydrothermal process of making nanometer TiO material2Coating the surface of natural sheet mineral kaolinite to obtain kaolinite-loaded nano TiO2The composite uvioresistant agent is suitable for the field of uvioresistant materials or ultraviolet shielding materials.
2. Background of the invention
2.1 ultraviolet concept
Ultraviolet (UV) is an electromagnetic wave having a wavelength of 200nm to 400 nm. The ultraviolet rays in the 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 the wavelength. Proper sunlight irradiation can increase oxygen content of organism 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
Figure BDA0002327638190000011
The short wave ultraviolet UVC is absorbed by the ozone layer, cannot reach the ground and has no effect on human bodies. Long-wave ultraviolet UVA causes photoaging of the skin, resulting in skin cancer. 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. Most skin damage is caused by UVB, which if exposed to UVB for a long time, causes erythema, inflammation, skin aging, and severe skin cancer.
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 very 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 in terms of heat resistance, stability, ultraviolet absorption range, toxicity, etc., which act only in a single wavelength band (UVA or UVB), and which may decompose and lose the sunscreen effect under the action of light, with a short period of effectiveness. 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).
Nano TiO 22As a widely used physical sun-screening agent, the principle of shielding ultraviolet rays is to absorb and scatter the ultraviolet rays, and the sun-screening agent 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, due to the nano TiO2The nano-particles have the characteristics of weak polarity, tiny nano-particles and high surface energy, and are in a thermodynamic unstable state and tend to agglomerate, so that the exertion of the nano-effect and the ultraviolet shielding effect is limited. And, in the skin care product or cosmetic manufacturing process, the nano TiO2The particles are difficult to disperse to the original particle size, the ultraviolet absorption effect in 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, nano TiO2As an inorganic sunscreen, there are the following major problems:
(1) agglomeration problem: nano TiO 22The surface energy of (a) is high and the particles tend to agglomerate.
(2) The problem of delamination: the emulsion density of the sunscreen product is aboutIs 0.96-1.1g/cm3And nano TiO2Has a density of about 3.8 to 4.3g/cm3So that the nano TiO with high density is used2When the emulsifier is added, the precipitation is easy to occur, and the layering phenomenon is generated. This delamination phenomenon greatly limits the nano-TiO2The using efficiency of the material can not 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: nano TiO in sunscreen products2The sweat easily gathers at the human skin horny layer, the hair follicle sebaceous gland opening and the wrinkle, and the size of the human facial pores is generally 20 mu m, so the sweat is not easy to be secreted, and the skin infection is easily caused.
(4) The aesthetic problem is that: due to the nanometer TiO2The agglomeration of the ingredients may cause unnatural whitening when applied to the skin, which may affect the aesthetic appearance.
(5) The price problem is as follows: due to the nanometer TiO2Can not be directly mixed with common cosmetics for use, and in order to overcome the layering phenomenon of dispersion liquid when used alone, a small-sized special container and a device are needed in actual use, so that the production and use costs of physical sunscreen products are greatly increased, the market price of the products is generally higher, and the using amount of the products is limited.
2.3 nanometer TiO2State of the art of preparation
According to the state of the raw materials and different preparation processes, the nano TiO2The preparation method mainly comprises three types of liquid phase method, solid phase method and gas phase method. 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. Currently preparing nano TiO2The liquid phase method and the solid phase method are mainly adopted, and the advantages and disadvantages are shown in Table 2.
TABLE 2 Nano TiO2Advantages and disadvantages of the principal preparation method
Figure BDA0002327638190000031
2.4 mineral-loaded nano TiO2Current state of the art for the study of composite anti-UV agents
Solves the problem of nano TiO2The problems of agglomeration, delamination and the like can be started from two aspects: firstly, a certain preparation method is adopted to prepare nano TiO2Modifying to obtain nanometer TiO2Regulating and controlling the appearance and the like; firstly, the mineral is used as a carrier to load the nano TiO2. The leading research progress of the predecessors was as follows:
CN 107604644A discloses a hydrothermal method for preparing illite-loaded nano TiO2The method of compounding ultraviolet screening agent features that in hydrothermal system of titanium sulfate and ammonia water, nanometer level TiO is realized2The dispersion and the combination on the surface of the illite are sufficient. The composite powder has good ultraviolet shielding performance, and can be widely applied to the protection fields of textile finishing, paint and the like.
CN 107012728A discloses a sunscreen agent loaded with nano titanium dioxide prepared by taking kaolinite, polyethylene glycol and nano titanium dioxide as raw materials and adopting a mechanochemical method, the preparation process has no waste water, the process equipment is simple, the operation is simple and convenient, and the sunscreen and anti-aging performance of decorative paper can be improved by using the sunscreen agent in the production of decorative paper.
CN 103773085A discloses a functional mica pigment processing technique, which takes sericite as raw material, tetravalent titanium salt as titanium source to coat a mica substrate, zinc sulfate solution is selected to be added into the coated TiO2Adding calcium hydroxide while stirring to coat TiO2Filtering, washing, drying and calcining the sericite slurry. The functional mica has better glossiness, can insulate heat and has excellent ultraviolet shielding performance.
Shenhongling, Zhengshuirin, etc. (2009) mentioned the use of hydrolytic precipitation method to coat nano TiO on the surface of calcined kaolin2Preparation of TiO2The calcined kaolin composite powder material has good uvioresistant performance under the proper preparation conditions, namely, when the coating amount is 9 percent, the dosage of hydrochloric acid is 0.05ml/g, and the dosage of ammonium sulfate is 1.75 ml/g.
From above to belowAs can be seen from the above description, the mineral-loaded nano TiO is currently concerned2The preparation method of the anti-ultraviolet agent is mainly a liquid phase method, wherein Jianjiang and the like (2018) adopt a hydrothermal method to prepare nano TiO2The illite composite powder material. However, according to the search of the inventor, no kaolinite-loaded nano TiO prepared by a hydrothermal method is currently available2The technical results of the composite uvioresistant agent are reported.
3. Technical scheme
The invention aims to load nano TiO by taking natural flaky mineral kaolinite with a layered structure as a raw material2Preparing a composite uvioresistant agent or ultraviolet shielding material to overcome the defects of the existing nano TiO2Easy agglomeration, easy delamination, poor dispersibility and the like, improves the sun-screening and ultraviolet-screening performances, improves the beautiful effect, prevents the whitening phenomenon, improves the use efficiency and reduces 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: the mineral crystal has a layered structure and two-dimensional habit crystals, is mainly in a fine scaly shape, is non-toxic and harmless, and is rich in mineral raw materials.
(2) Nano TiO 22Selection of a preparation method: 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) Nano TiO 22The hydrothermal method preparation process comprises the following steps: on the basis of the work in the step (2), the hydrothermal method for preparing the nano TiO is further determined by experiments2The process conditions of (1).
(4) Kaolinite loaded nano TiO2The preparation process of the composite uvioresistant agent comprises the following steps: on the basis of the work in the step (3), further experiments confirm that the kaolinite load nano TiO is prepared by a hydrothermal method2The technological conditions of the composite uvioresistant agent.
The specific technical scheme is as follows:
3.1 selection of Carrier mineral raw materials
Kaolinite is a 1:1 type dioctahedral lamellar structureAn aluminosilicate mineral having a crystal formula of Al4[Si4O10](OH)8Theoretical chemical composition is Al2O341.2％，SiO248.0% and H2And (4) O10.8%. Kaolinite is a triclinic system, the crystal structure of which is composed of a layer of SiO4]Tetrahedron and a layer of [ AlO6]Octahedron structure, with a typical 1:1 layered structure. Restricted by a crystal layer-shaped structure, kaolinite generally takes the shape of scales, books, pseudo hexagonal plates and the like; the kaolinite has stable chemical property, no toxicity and no harm, and is suitable for being used as nano TiO2The requirement of carrier minerals. It should be noted that the crystal structure of kaolinite is similar to that of dickite, but is different from that of dickite in terms of homogeneity, multiple image variants, geological causes, occurrence and the like, and is therefore different mineral species.
Fig. 1 is an X-ray powder diffraction pattern (XRD) of the kaolinite sample used in the present invention, and it can be seen that the diffraction peak of the kaolinite is relatively sharp, which indicates that the crystal structure of the raw material kaolinite is complete, the crystalline state is good, and is substantially consistent with the kaolinite standard card (PDF: 14-0164), and the characteristic diffraction peak is:
Figure BDA0002327638190000051
clearly distinct from dickite. In summary, the kaolinite used in the invention is pure, but a quartz diffraction peak appears on an XRD spectrogram, which indicates that the kaolinite also contains a small amount or trace of quartz minerals and the like.
Table 3 shows the results of X-ray fluorescence spectrum (XRF) detection of chemical components of the kaolinite sample used in the present invention, and it can be seen that the kaolinite sample has chemical components with weight percentage (%) close to the theoretical components, and has very low contents of other impurity components, and contains no toxic and harmful impurity components for human body. The result of XRD analysis is combined, so that the experimental sample is relatively pure, belongs to the kaolinite monomineral aggregate and accords with TiO2Selection conditions of the carrier mineral raw material.
TABLE 3X-ray fluorescence Spectroscopy (XRF) measurements of the chemical composition of kaolinite samples (in weight percent,%)
Substance(s) SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2O Na2O MnO P2O5 SO3 H2O
Content (wt.) 44.21 35.76 0.89 0.46 0.02 0.16 0.87 1.01 — 0.8 0.62 15.17
3.2 nanometer TiO2Selection of preparation methods
According to related documents, by comparing the advantages and the disadvantages of the five methods in table 2, the hydrothermal method can directly obtain powder with good crystallinity in one step, high-temperature roasting crystallization is not needed, secondary growth of crystal grains is avoided, and hard agglomeration is formed, so that the hydrothermal method is adopted for preparation, and an ultraviolet-visible spectrophotometer is adopted for detection and analysis of the ultraviolet shielding performance, and the result is shown in fig. 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, industrial TiO2Although the paint also has certain ultraviolet resistance, the ultraviolet shielding performance is far inferior to that of nano TiO2. 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 FIG. 2, the ultraviolet shielding rate of industrial titanium dioxide just reaches 90%, belongs to b-grade and cannot meet the requirement of an ultraviolet shielding material, and the nano TiO prepared by a hydrothermal method2The ultraviolet shielding rate of the composite material is more than 90 percent, belongs to a grade a, and meets the requirement of the invention.
3.3 nanometer TiO2Hydrothermal preparation process
The invention further determines the hydrothermal method to prepare the nano TiO through experiments2The process conditions are as follows:
(1) preparing a titanium sulfate solution: selecting titanium sulfate (Ti (SO)4)2) Preparing titanium sulfate into 0.3-1.2 mol/l titanium sulfate solution as a titanium source, and magnetically stirring for 30min to fully dissolve the titanium sulfate solution;
(2) preparing a titanium sulfate-urea mixed solution: adding a certain amount of urea into a titanium sulfate solution to ensure that the amount ratio of the urea to the titanium sulfate is 1-3: 1, and fully stirring for 1-2 h;
(3) hydrothermal reaction: pouring the titanium sulfate-urea mixed solution into a polytetrafluoroethylene reaction kettle (the solution accounts for 70-80% of the volume of the kettle), placing the sealed hydrothermal kettle at the hydrothermal temperature of 140-200 ℃ for full reaction for 2-8 h, and after the reaction is finished, naturally cooling, pouring out supernatant in the reaction kettle to obtain a kettle bottom reaction product;
(4) washing to remove impurities: carrying out centrifugal washing on the reaction product by adopting a centrifugal washing device, washing by using distilled water twice, and washing by using absolute ethyl alcohol twice to remove impurities;
(5) drying the materials: transferring the reaction product after washing and impurity removal into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 4-6 h, thus obtaining the nano TiO2And (3) powder.
FIG. 3 shows the hydrothermal preparation of nano TiO2The X-ray powder crystal diffraction spectrum shows that three standard strong peaks with sharp peak shapes and high intensity appear in the range of 20-50 DEG diffraction angle, namely
Figure BDA0002327638190000061
Figure BDA0002327638190000062
This is in conjunction with nano TiO2The standard PDF cards (21-1272) are substantially coincident. Considering that the characteristic peaks appearing in the whole angle diffraction range are relatively sharp, the nano TiO is shown2The crystal form of the sample is better, and the crystallization is more complete. Meanwhile, no miscellaneous peak which can not correspond to the standard card appears in the diffraction pattern, which indicates that the purity of the sample is higher.
FIG. 4 shows the hydrothermal preparation of nano TiO2The analysis photo of the scanning electron microscope shows that the nano TiO is2The powder crystal grains are spherical or quasi-sphericalHas the characteristics of nano particles, the particle size is 30 nm-50 nm, but the obvious agglomeration phenomenon appears.
3.4 kaolinite loaded nano TiO2Preparation process of composite uvioresistant agent
On the basis of the work, further experiments confirm that the kaolinite load nano TiO is prepared by a hydrothermal method2The process conditions of the composite uvioresistant agent are as follows:
(1) preparing a titanium sulfate solution: selecting titanium sulfate (Ti (SO)4)2) Preparing titanium sulfate into 0.3-1.2 mol/l titanium sulfate solution as a titanium source, and magnetically stirring for 30min to fully dissolve the titanium sulfate solution;
(2) preparing a titanium sulfate-urea-kaolinite mixed solution: adding a certain amount of urea into a titanium sulfate solution to enable the amount ratio of urea to titanium sulfate substances to be 1-3: 1, fully stirring for 1-2 h, and adding a proper amount of kaolinite to enable TiO in a mixed system to be TiO2The mass ratio of the kaolin to the kaolinite is 0.5-2, the mixture is fully stirred for 1-2 h, and ultrasonic oscillation is carried out for 30 min;
(3) hydrothermal reaction: pouring the titanium sulfate-urea-kaolinite mixed solution into a polytetrafluoroethylene reaction kettle (the solution accounts for 70-80% of the volume of the kettle), placing the sealed hydrothermal kettle at the hydrothermal temperature of 140-200 ℃ for fully reacting for 2-8 h, and after the reaction is finished, naturally cooling, pouring out supernatant in the reaction kettle to obtain a kettle bottom reaction product;
(4) washing to remove impurities: carrying out centrifugal washing on the reaction product by adopting a centrifugal washing device, washing by using distilled water twice, and washing by using absolute ethyl alcohol twice to remove impurities;
(5) drying the materials: transferring the reaction product after washing and impurity removal into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 4-6 h, thus obtaining the kaolinite loaded nano TiO2And (3) a composite anti-ultraviolet agent.
4. Technical advantages
(1) The effect is obvious. The invention takes kaolinite as a carrier and adopts a hydrothermal method to prepare kaolinite-loaded nano TiO2Composite uvioresistant agent, and composite material thereof is more than nano TiO prepared independently2Has better ultraviolet resistance or ultravioletShielding performance, better dispersibility in solvent and higher transmittance to visible light, solves the problem of nano TiO2The agglomeration, the layering, the beauty and the like.
(2) The safety is good. The kaolinite used in the invention is natural mineral, and is nontoxic and pollution-free. Preparation of nano TiO2The raw material reagents used in the process are nontoxic, safe and reliable.
(3) The process is simple. The hydrothermal method used in the invention is simple to operate and convenient to 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 kaolinite load nanometer TiO prepared by the invention2The composite uvioresistant agent better solves the problem of the prior nano TiO2The method has important significance for the development of the ultraviolet-resistant 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 kaolinite sample adopted by the invention.
FIG. 2: nano TiO prepared by hydrothermal method2Ultraviolet shielding performance (Abs-absorbance, T-ultraviolet shielding rate).
FIG. 3: nano TiO prepared by hydrothermal method2The X-ray powder crystal diffraction spectrum of (1).
FIG. 4: nano TiO prepared by hydrothermal method2Scanning Electron Microscope (SEM) photograph of (a).
FIG. 5: kaolinite and nano TiO2And kaolinite supported nano TiO2And an X-ray powder crystal diffraction spectrum of the composite uvioresistant agent.
FIG. 6: kaolinite (a) and kaolinite-supported nano TiO2Scanning electron microscope analysis photo of the anti-ultraviolet agent (b).
FIG. 7: kaolinite and industrial TiO2Nano, nanoTiO2Kaolinite loaded nano TiO2Ultraviolet-visible light spectrum contrast diagram (Abs-absorbance, T-ultraviolet shielding rate) of the composite uvioresistant agent.
6. Detailed description of the preferred embodiments
Example 1: kaolinite loaded nano TiO2Composite uvioresistant agent and its prepn process
The kaolinite is prepared by taking natural flaky mineral kaolinite as a carrier mineral raw material, wherein the kaolinite is relatively pure (figure 1), crystals are in irregular flaky shapes, the sizes of the flakes are 0.5-2 mu m (figure 6a), the chemical components of the kaolinite are shown in a table 3, and a hydrothermal method is adopted to prepare the kaolinite-loaded nano TiO2The preparation process of the composite uvioresistant agent comprises the following 5 steps:
(1) preparing a titanium sulfate solution: selecting titanium sulfate (Ti (SO)4)2) Preparing titanium sulfate into 0.3-1.2 mol/l titanium sulfate solution as a titanium source, and magnetically stirring for 30min to fully dissolve the titanium sulfate solution;
(2) preparing a titanium sulfate-urea-kaolinite mixed solution: adding a certain amount of urea into a titanium sulfate solution to enable the amount ratio of urea to titanium sulfate substances to be 1-3: 1, fully stirring for 1-2 h, and adding a proper amount of kaolinite to enable TiO in a mixed system to be TiO2The mass ratio of the kaolin to the kaolinite is 0.5-2, the mixture is fully stirred for 1-2 h, and ultrasonic oscillation is carried out for 30 min;
(3) hydrothermal reaction: pouring the titanium sulfate-urea-kaolinite mixed solution into a polytetrafluoroethylene reaction kettle (the solution accounts for 70-80% of the volume of the kettle), placing the sealed hydrothermal kettle at a hydrothermal temperature of 180 ℃ for full reaction for 2-8 h, and after the reaction is finished, naturally cooling, pouring out supernatant in the reaction kettle to obtain a kettle bottom reaction product;
(4) washing to remove impurities: carrying out centrifugal washing on the reaction product by adopting a centrifugal washing device, washing by using distilled water twice, and washing by using absolute ethyl alcohol twice to remove impurities;
(5) drying the materials: transferring the reaction product after washing and impurity removal into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 4-6 h, thus obtaining the kaolinite loaded nano TiO2And (3) a composite anti-ultraviolet agent.
The result of the detectionIt is shown that the kaolinite obtained by the method of this example supports nano-TiO2The composite uvioresistant agent has the following characteristics:
(1) FIG. 5 shows kaolinite and nano TiO2And kaolinite supported nano TiO2The X-ray powder diffraction spectrum of the composite uvioresistant agent can be seen, and the composite uvioresistant agent, kaolinite and nano TiO can be seen2In contrast, kaolinite supported nano TiO2Kaolinite and nano TiO can be seen in the XRD pattern of the composite uvioresistant agent2The characteristic peaks of the two substances are generated because no new peak is generated, which indicates that the two substances are physically compounded.
(2) FIG. 6 shows kaolinite (a) and kaolinite-supported nano TiO2Scanning Electron Microscope (SEM) photo of the uvioresistant agent (b) shows that nano TiO is loaded on the surface of the kaolinite flake2The particles are uniform in particle size distribution, are spherical, have the size of about 30-50 nm, and obviously improve the agglomeration phenomenon.
(3) FIG. 7 is kaolinite, industrial TiO2TiO 2 nanoparticles2Kaolinite loaded nano TiO2The ultraviolet-visible light spectrum contrast chart of the composite uvioresistant agent can show that: first, kaolinite has poor UV resistance and industrial TiO2Secondly, the performance requirements of the anti-ultraviolet agent are not met. Second, with industrial TiO2In contrast, nano TiO2The absorbance of the ultraviolet region is obviously increased, the uvioresistant performance is excellent, the ultraviolet shielding rate can reach 95 percent, the transmittance of the visible light region is lower, and the whiteness is proved to be higher than that of industrial TiO2And decreases. Third, with nano TiO2Compared with the prior art, the kaolinite is loaded with nano TiO2The absorbance of the uvioresistant agent in the ultraviolet region is further improved, the ultraviolet shielding rate is close to 99 percent, which shows that the uvioresistant performance is excellent, and the transmittance of the uvioresistant agent to visible light is better than that of the prepared nano TiO2The transparency was good.
The detection results show that the kaolinite loaded nano TiO obtained by the embodiment of the invention2The composite uvioresistant agent can overcome the defects of the existing nano TiO2Easy agglomeration and the like, obviously improves the nano TiO2The ultraviolet-resistant or ultraviolet-resistant shielding material has good market prospect and social and economic benefits.
Fund project: the work subsidies national science fund projects (41972039, 41572038) and scientific research projects (16TD0011) funded by the university and development hall in Sichuan.

Claims (1)

1. Kaolinite loaded nano TiO2A composite uvioresistant agent is prepared from kaolinite as carrier by hydrothermal method2The composite uvioresistant agent is characterized in that:
(1) preparing a titanium sulfate solution: selecting titanium sulfate (Ti (SO)4)2) Preparing titanium sulfate into 0.3-1.2 mol/l titanium sulfate solution as a titanium source, and magnetically stirring for 30min to fully dissolve the titanium sulfate solution;
(2) preparing a titanium sulfate-urea-kaolinite mixed solution: adding a certain amount of urea into a titanium sulfate solution to enable the amount ratio of urea to titanium sulfate substances to be 1-3: 1, fully stirring for 1-2 h, and adding a proper amount of kaolinite to enable TiO in a mixed system to be TiO2The mass ratio of the kaolin to the kaolinite is 0.5-2, the mixture is fully stirred for 1-2 h, and ultrasonic oscillation is carried out for 30 min;
(3) hydrothermal reaction: pouring the titanium sulfate-urea-kaolinite mixed solution into a polytetrafluoroethylene reaction kettle (the solution accounts for 70-80% of the volume of the kettle), placing the sealed hydrothermal kettle at the hydrothermal temperature of 140-200 ℃ for fully reacting for 2-8 h, and after the reaction is finished, naturally cooling, pouring out supernatant in the reaction kettle to obtain a kettle bottom reaction product;
(4) washing to remove impurities: carrying out centrifugal washing on the reaction product by adopting a centrifugal washing device, washing by using distilled water twice, and washing by using absolute ethyl alcohol twice to remove impurities;
(5) drying the materials: transferring the reaction product after washing and impurity removal into a drying device, wherein the drying temperature is 105 ℃, and the drying time is 4-6 h, thus obtaining the kaolinite loaded nano TiO2And (3) a composite anti-ultraviolet agent.
The kaolinite is a 1:1 type dioctahedral lamellar structure aluminosilicate mineral with a crystal chemical formula of Al4[Si4O10](OH)8Identification of X-ray powder diffraction analysisThe definite characteristic peak is
Figure FDA0002327638180000011
Figure FDA0002327638180000012
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