CN101618850B - Preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite - Google Patents
Preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite Download PDFInfo
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- CN101618850B CN101618850B CN2009100413906A CN200910041390A CN101618850B CN 101618850 B CN101618850 B CN 101618850B CN 2009100413906 A CN2009100413906 A CN 2009100413906A CN 200910041390 A CN200910041390 A CN 200910041390A CN 101618850 B CN101618850 B CN 101618850B
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- ultraviolet ray
- zirconium oxide
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- zinc zirconium
- oxide nanocomposite
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Abstract
The invention discloses a preparation method of an anti-ultraviolet ray zinc zirconium oxide nanocomposite, which comprises the steps of adding a cationic surfactant-cetyltrimethyl ammonium bromide in mixed solution of Zn(NO3)2 and ZrOCl2 with the molar ratio of 100:10-100:1, dripping NaOH solution or urea solution under stirring within the range from room temperature to 85 DEG C, carrying out co-precipitation reaction, to obtain a product precursor slurry, transferring the slurry into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-200 DEG C for 0.5-4h, washing and drying a product after the completion of the hydrothermal reaction, thereby obtaining the anti-ultraviolet ray zinc zirconium oxide nanocomposite. The anti-ultraviolet ray zinc zirconium oxide enhances the ability of absorbing ultraviolet ray of the material and further enhances the shielding effect for the ultraviolet ray, and the preparation method adopts the hydrothermal reaction for processing the precursor of the nano material, thereby avoiding the sintering phenomenon among the particles and overcoming the adverse effects on the material caused by high-temperature calcination.
Description
Technical field
The present invention relates to a kind of preparation method of ultraviolet light composite powder nano material, particularly relate to the preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite, belong to composite nano powder material field.
Background technology
Commercially available ultraviolet light material mainly is divided into inorganic matter ultraviolet light screener and organic matter ultraviolet light screener at present, because inorganic matter ultraviolet light screener has chemical inertness, safe in utilization, all be higher than organic matter ultraviolet light screener aspect heat endurance and the solvent resistance, thus the exploitation low toxicity, inorganic matter ultraviolet light screener receives more concern efficiently.Wherein topmost inorganic matter ultraviolet light screener is exactly zinc oxide and titanium dioxide, but the price of titanium dioxide is more expensive, has limited its use.And nano level zinc oxide only has absorption (" cosmetic chemistry language technology complete works " the bright firm work of first volume P618-620 China Light Industry Press fur coat) at the 300-380nm wave band.
At present, the main method of preparation inorganic matter ultraviolet light screener is a sol-gel, precipitation, hydrolysis, all to pass through high-temperature calcination when these methods were handled the predecessor of nano material in the later stage, make predecessor resolve into required product, but in calcination process, between the nano particle sintering can take place, thereby influenced the character of product.
Chinese invention patent CN 1260366 discloses the modified nm zinc oxide UV ray shielding/absorbing material, adopt ultrasonic micro-emulsion method for preparing nano zinc oxide ultraviolet light material, make by the nano oxidized zinc surface coated non-ionic surfactant modifier that mixes through magnesia, but this method adopts ultrasonic microemulsion method, the cost height is difficult to large-scale production.
Chinese invention patent application CN 101429348 discloses a kind of titanium dioxide-zinc oxide composite powder preparation methods, and the subcarbonate by zinc stops the sintering between the particle in the decomposition on titanium dioxide granule surface.But this composite photostability be still waiting to improve.And nano level titanium dioxide price height, thereby improved preparation cost.
Chinese invention patent CN 1246443 discloses a kind of nanometer Zinc oxide powder and preparation method's bag of particles cladded by metallic compound on surface, this material has excellent UV Absorption characteristic, but the projection ratio for visible light is low, and is difficult for evenly disperseing in the lipophile body.
Summary of the invention
The shortcoming that the objective of the invention is the customer service prior art, a kind of preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite is provided, to improve the screening ability of material to ultraviolet light, this material not only can shield ultraviolet light efficiently, and heat endurance and chemical stability height, colourless, nontoxic, anti-solvent, good with various base material compatibilities, need only add and just can reach on a small quantity the requirement that shields ultraviolet light, and not influence material to the light transmission of visible light with avoid sintering phenomenon between the particle.
The present invention is to provide a kind of zinc zirconium oxide composite nano materials, under the effect of surfactant, adopt the method for co-precipitation-hydro-thermal to prepare the zinc zirconium oxide composite with ultraviolet light function.Concrete method is: the Zn (NO that with zinc zirconium mol ratio is 100: 10～100: 1
3)
2With ZrOCl
2Solution (Zn (NO wherein
3)
2Concentration be 0.5～2mol/L
-1), other adds the cationic surfactant softex kw, be heated to uniform temperature (room temperature～80 ℃), under agitation drip NaOH or 0.5～4mol/L urea that concentration is 0.5～4mol/L, reaction a period of time (after 0.25～4.h), changes the slurry of gained over to hydrothermal reaction kettle and carries out hydro-thermal reaction (reaction temperature is 120～200 ℃, reaction time 0.5～4h, hydro-thermal is washed drying after finishing to product with ethanol.
Ultraviolet shielded effect testing method is: (PVA) is dissolved in the deionized water with the polymer binder polyvinyl alcohol, and the mass ratio of the two is 1: 10, obtains mixed liquor A; In addition powder body material is scattered in the deionized water, the mass ratio of powder body material and deionized water is 1: 400, obtains mixed liquid B; Two kinds of mixed liquors of A, B are fully mixed with mass ratio at 1: 2, get resulting mixed liquor 0.3ml, be coated on equably on the transparent sheet of 25mm*25mm, the dry back of band has carried out testing (quality of uvioresistant material is about 0.08g in being every square metre) with the UV-265 spectrophotometer to the ultraviolet light shield effectiveness of material.
The present invention's advantage compared with prior art is:
(1) finds that by the Ma Erwen grain size analysis mixing of Zirconium oxide can make the particle diameter of powder body material reduce, mixing of a small amount of zr element, make the lattice of zinc oxide produce a large amount of defectives, the generation of lattice defect has hindered further growing up of crystal grain, so particle diameter reduces.And, the defective of material grains is increased along with the mixing of zirconium, and material is strengthened ultraviolet absorption, ultraviolet shield effectiveness is strengthened.
(2) the present invention combines (being co-precipitation-hydro-thermal method) by coprecipitation with hydro-thermal method, adopts hydro-thermal reaction that the predecessor of nano material is handled, thereby has avoided the sintering phenomenon between the particle, has overcome the adverse effect of high-temperature calcination to material production.
(3) the composite nano materials heat endurance and the chemical stability height of the present invention's preparation, colourless, nontoxic, anti-solvent, good with various base material compatibilities, and zirconium mix the energy gap that can not change semi-conducting material (referring to zinc oxide), in the visible region, material does not change the absorption of visible light, and is little to the light transmission influence of visible light.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment, but embodiments of the invention are not limited thereto.
Embodiment 1
75ml Zn (NO
3)
2And ZrOCl
2Mixed solution, Zn (NO
3)
2With ZrOCl
2Mol ratio be 100: 1, Zn (NO
3)
2Concentration in mixed solution is 0.5mol/L, in this solution, add cationic surfactant softex kw 0.14g, under stirring at room, drip 40ml, 1mol/L NaOH solution, drip and finish, continue to stir 0.5h, change slurry over to hydrothermal reaction kettle, 120 ℃ of hydrothermal treatment consists 0.5h, naturally cool to room temperature, with the ethanol washing, 45 ℃ of dryings make the composite nano powder material again.By the test of Ma Erwen Particle Size Analyzer to its particle diameter, its particle diameter in wavelength is the 300-370nm scope, is 86% to the shielding rate of ultraviolet light in the 60-110nm scope, in wavelength is the 220-300nm scope, is 95% to the shielding rate of ultraviolet light.
Prepared zinc zirconium composite nano materials to the test result of ultraviolet screener and simple zinc oxide to the test result contrast of ultraviolet screener as following table 1:
Table 1
| Aggregate particle size/(nm) | Ultraviolet light shield ranges (nm) | Shielding rate (%) | |
| Zinc oxide | 110-160 | 300-380 | 85 |
| Zinc zirconium oxide | 60-110 | 220-300 300-380 | 98 95 |
From table 1 contrast as can be seen, zinc zirconium composite nano oxide is better than simple zinc oxide to ultraviolet shield effectiveness to ultraviolet shield effectiveness, and compare other method (sol-gel by precipitation-Hydrothermal Preparation, precipitation, hydrolysis) can under lower temperature, (120 ℃) just prepare ZnO, can avoid the sintering that Yin Gaowen causes in preparation process with certain crystal formation.
The zirconium owing to mix in zinc oxide increases the defective of material grains, and material is strengthened ultraviolet absorption, and material strengthens ultraviolet shield effectiveness.But zirconium mix the energy gap that can not change semi-conducting material (zinc oxide), so in the visible region, material does not change the absorption of visible light, little to the light transmission influence influence of visible light.
Embodiment 2
75ml Zn (NO
3)
2And ZrOCl
2Mixed solution, Zn (NO
3)
2And ZrOCl
2Mol ratio be 100: 10, Zn (NO
3)
2Concentration in mixed solution is 2mol/L, adds cationic surfactant softex kw 0.55g in this solution, is heated to 70 ℃, and under agitation drip 100ml, concentration is 4mol/L NaOH solution, drips to finish, and continues to stir 4h, change slurry over to hydrothermal reaction kettle, 200 ℃ of hydrothermal treatment consists 4h naturally cool to room temperature, wash with ethanol again, 45 ℃ of dryings make the composite nano powder material.By the test of Ma Erwen Particle Size Analyzer to its particle diameter, its particle diameter in wavelength is the 300-370nm scope, is 87% to the shielding rate of ultraviolet light in the 80-130nm scope, in wavelength is the 220-300nm scope, is 94% to the shielding rate of ultraviolet light.
Embodiment 3
75ml Zn (NO
3)
2And ZrOCl
2Mixed solution, Zn (NO
3)
2And ZrOCl
2Mol ratio be 100: 5, Zn (NO
3)
2Concentration be 1mol/L, in this solution, add cationic surfactant softex kw 0.27g, be heated to 40 ℃, and under agitation drip 80ml, concentration is 3mol/L NaOH solution, drips to finish, and continues to stir 1h, change slurry over to hydrothermal reaction kettle, 150 ℃ of hydrothermal treatment consists 2h naturally cool to room temperature, wash with ethanol again, 45 ℃ of dryings make the composite nano powder material.By the test of Ma Erwen Particle Size Analyzer to its particle diameter, its particle diameter in wavelength is the 300-370nm scope, is 93% to the shielding rate of ultraviolet light in the 70-120nm scope, in wavelength is the 220-300nm scope, is 96% to the shielding rate of ultraviolet light.
Embodiment 4
75ml Zn (NO
3)
2And ZrOCl
2Mixed solution, Zn (NO
3)
2And ZrOCl
2Mol ratio be 100: 1, Zn (NO
3)
2Concentration be 0.5mol/L, in this solution, add cationic surfactant softex kw 0.13g, be heated to 85 ℃, and under agitation drip 40ml, concentration is the 2mol/L urea liquid, drips to finish, and continues to stir 3h, change slurry over to hydrothermal reaction kettle, 120 ℃ of hydrothermal treatment consists 0.5h naturally cool to room temperature, wash with ethanol again, 45 ℃ of dryings make the composite nano powder material.By the test of Ma Erwen Particle Size Analyzer to its particle diameter, its particle diameter in wavelength is the 300-370nm scope, is 93% to the shielding rate of ultraviolet light in the 60-100nm scope, in wavelength is the 220-300nm scope, is 96% to the shielding rate of ultraviolet light.
Embodiment 5
75ml Zn (NO
3)
2And ZrOCl
2Mixed solution, Zn (NO
3)
2And ZrOCl
2Mol ratio be 100: 10, Zn (NO
3)
2Concentration be 1.5mol/L, in this solution, add cationic surfactant softex kw 0.41g, be heated to 85 ℃, and under agitation drip 100ml, concentration is the 4mol/L urea liquid, drips to finish, and continues to stir 3h, change slurry over to hydrothermal reaction kettle, 200 ℃ of hydrothermal treatment consists 2h naturally cool to room temperature, wash with ethanol again, 45 ℃ of dryings make the composite nano powder material.By the test of Ma Erwen Particle Size Analyzer to its particle diameter, its particle diameter in wavelength is the 300-370nm scope, is 90% to the shielding rate of ultraviolet light in the 80-130nm scope, in wavelength is the 220-300nm scope, is 95% to the shielding rate of ultraviolet light.
Claims (4)
1. the preparation method of an anti-ultraviolet ray zinc zirconium oxide nanocomposite is characterized in that: the Zn (NO that in mol ratio is 100: 10～100: 1
3)
2And ZrOCl
2Mixed solution in add the cationic surfactant softex kw; The mole of softex kw is Zn (NO
3)
21% of mole in room temperature～85 ℃, stirs down, and the NaOH solution or the concentration that drip concentration and be 0.5～4mol/L are the urea liquid of 1～4mol/L, carry out coprecipitation reaction; Described Zn (NO
3)
2And ZrOCl
2Mixed solution and the volume ratio of NaOH solution or urea liquid be 15: 8～15: 20, obtain product predecessor slurry behind reaction 0.25～4h, described slurry is changed in the hydrothermal reaction kettle, in temperature is hydro-thermal reaction 0.5～4h under 120～200 ℃ of conditions, after hydro-thermal finishes, product is through washing, and drying makes anti-ultraviolet ray zinc zirconium oxide nanocomposite;
Described Zn (NO
3)
2Concentration in mixed solution is 0.5～2mol/L.
2. the preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite according to claim 1, it is characterized in that: the concentration of described NaOH is 2～3mol/L.
3. the preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite according to claim 1, it is characterized in that: the concentration of described urea liquid is 2～3mol/L.
4. the preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite according to claim 1 is characterized in that; Described product is meant that through washing product washs through ethanol.
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|---|---|---|---|---|
| CN101898747A (en) * | 2010-04-20 | 2010-12-01 | 华南理工大学 | Preparation method of zinc/cerium composite powder nano material capable of shielding ultraviolet rays |
| CN107955321B (en) * | 2017-12-08 | 2021-04-30 | 上海瀚氏模具成型有限公司 | Anti-ultraviolet plastic for automotive upholstery |
| CN115028191B (en) * | 2022-07-26 | 2024-03-01 | 宣城晶瑞新材料有限公司 | Preparation method of composite nano zinc oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103907A1 (en) * | 2003-05-21 | 2004-12-02 | Hanwha Chemical Corporation | Metal oxide solid solution, preparation and use thereof |
| CN1562762A (en) * | 2004-04-22 | 2005-01-12 | 上海交通大学 | Method for preparing nano zinc oxide in monodisperse, with no agglomeration and strong ultraviolet absorption |
| CN1785817A (en) * | 2005-12-21 | 2006-06-14 | 四川大学 | Preparation of shielding ultra violest ray nano-ZnO/TiO2 composite powder |
-
2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103907A1 (en) * | 2003-05-21 | 2004-12-02 | Hanwha Chemical Corporation | Metal oxide solid solution, preparation and use thereof |
| CN1562762A (en) * | 2004-04-22 | 2005-01-12 | 上海交通大学 | Method for preparing nano zinc oxide in monodisperse, with no agglomeration and strong ultraviolet absorption |
| CN1785817A (en) * | 2005-12-21 | 2006-06-14 | 四川大学 | Preparation of shielding ultra violest ray nano-ZnO/TiO2 composite powder |
Non-Patent Citations (2)
| Title |
|---|
| 李蕾，等.影响纳米锌铝复合氧化物紫外吸收性能的因素.《北京化工大学学报》.2002,第29卷(第2期),83-87. * |
| 许国志,等.双金属复合氧化物的结构与紫外阻隔性能.《应用化学》.1999,第16卷(第5期),106-108. * |
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