CN1565977A - Process for preparing nano zinc oxide - Google Patents
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Abstract
The invention relates to a process for preparing nano zinc oxide wherein zinc acetate alcoholysis reaction is employed to couple the formation of zinc oxide and esterification reaction between acetates and ethanol, thus obtaining nana zinc oxide powder with double dispersibility.
Description
Technical Field
The invention relates to a preparation method of zinc oxide, in particular toa preparation method of nano zinc oxide.
Background
Zinc oxide powder, especially nano zinc oxide, is an important industrial raw material, and is widely used in many fields due to its excellent photoelectric properties and low price, for example: can be used for rubber products, glass, magneto-optical recording materials, sensors, sunscreen cream, antibacterial agents, sterilizing agents, deodorant agents, wound healing promoters, anticancer drugs and the like.
The commonly used method for preparing nano zinc oxide is a precipitation method. For example, as disclosed in the patent publication nos. 1396117, 1384057, and 1415545, basic zinc carbonate powder is obtained by adding carbonate, ammonium bicarbonate, ammonia water, urea, or other basic substances into a zinc-containing solution (such as a zinc sulfate solution), and then the basic zinc carbonate powder is calcined at 150 to 600 ℃ to obtain nano zinc oxide with an average particle size of 10 to 40 nm. However, the method needs high-temperature decomposition, so that the energy consumption is high, and the nano zinc oxide prepared by high-temperature calcination has more lattice defects, easily turns yellow in color and has poor conductivity, so that the application of the nano zinc oxide in cosmetics and electronic materials is limited; in addition, the produced zinc oxide nano-particles are easy to agglomerate and have poor dispersibility.
Another commonly used method for preparing nano zinc oxide is a hydrothermal method or a solvothermal method. As disclosed in the patent publication No. 1296916 and the patent publication No. 1296041, zinc hydroxide colloidal precipitate is prepared from a zinc salt solution and sodium hydroxide, and the zinc oxide nanoparticles having a particle size of 10 to 100nm can be prepared by hydrothermal or solvothermal reaction. The method solves the defects that zinc oxide crystallization needs a high-temperature process, the energy consumption is high, high agglomeration is easily generated among nano particles and the like in a precipitation method. However, the method needs to prepare the zinc hydroxide precursor first, and the increase of steps inevitably increases the complexity of the process and equipment, increases the cost and is not beneficial to industrial application.
In addition, the nano zinc oxide prepared by the two methods can only be dispersed in water, so that the application range of the zinc oxide is limited. Surface treatment of zinc oxide is generally employed to achieve good oil dispersion properties of the zinc oxide. As described in the patent publication No. 1245777, the nano zinc oxide coated with the surfactant is prepared by ultrasonic microemulsion, which can be dispersed in oil, but this preparation method has low yield, and the separation of the product is difficult, which is not easy to be industrialized.
Disclosure of Invention
The invention aims to: the defects of high energy consumption, easy agglomeration of zinc oxide nano particles, poor oil dispersibility, complex process and equipment and high cost in the prior art are overcome; preparing zinc oxide nano-particles which have water dispersibility and oil dispersibility (double dispersion characteristics), no agglomeration and white color; thereby providing a method for preparing the nano zinc oxide with simple process without high-temperature calcination.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of nano zinc oxide, which comprises the following steps:
putting fatty alcoholor an aqueous solution thereof and zinc acetate into an autoclave according to the proportion of 5-50 ml: 1g, heating to 80-300 ℃, and reacting for 2-48 hours; after the reaction is finished, cooling to room temperature; filtering out the precipitate, washing and drying by a conventional method to obtain the zinc oxide nano powder.
The filtrate and ethanol are mixed according to the volume ratio of 100: 0-0: 100 and can be used as a solvent for the next reaction.
The aliphatic alcohol comprises monohydric alcohol, dihydric alcohol and polyhydric alcohol, wherein the carbon content of the monohydric alcohol, the dihydric alcohol and the polyhydric alcohol is 1-10.
The monohydric alcohol is methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol or decanol.
The dihydric alcohol is ethylene glycol, propylene glycol or butanediol.
The polyol is glycerol.
The volume ratio concentration of the fatty alcohol in the fatty alcohol aqueous solution is 2-99 v%.
The invention provides a preparation method of nano zinc oxide, which takes zinc acetate and fatty alcohol as raw materials, and the zinc acetate and the fatty alcohol are subjected to alcoholysis reaction under the condition of solvothermal conditions to generate the nano zinc oxide, water and corresponding acetate, wherein the total reaction process is as follows:
the reaction mechanism of the method is as follows:
firstly, acetate and fatty alcohol are subjected to esterification reaction:
OH formed byesterification-Ions, with Zn in a solvent2+Ion reaction to generate hydroxyl complex ions of zinc:
or
As the reaction proceeds, Zn (OH) as a growth element of zinc oxide in the solution3 -Or Zn (OH)4 2-Gradually reach fullAnd, at this time, zinc oxide precipitation started:
or
The whole reaction process enables the generation of zinc oxide to be coupled with the esterification reaction of acetate and fatty alcohol, and the generated OH is moderate in esterification reaction speed and mild in reaction-Ions are uniformly distributed in the solvent, so that the nucleation and growth of the zinc oxide are well controlled, the zinc oxide can be uniformly separated out in the whole reaction solvent, and the zinc oxide nanoparticles with narrow particle size distribution can be obtained.
The nanometer zinc oxide prepared by the method of the invention shows a pure hexagonal zinc oxide diffraction image by XRD (X-ray diffraction) result, and does not have zinc acetate and other hetero-phase diffraction peaks. TEM (transmission electron microscope) analysis results (shown in figure 1) prove that the obtained nano zinc oxide has the particle size of about 30-100 nm, narrow distribution, uniform dispersion and no agglomeration. FT-IR (Fourier transform infrared spectroscopy) analysis shows that organic groups are combined on the surface of the obtained nano zinc oxide, the organic groups are acetate and used fatty alcohol, and the organic groups are combined with a dangling bond and an unsaturated bond on the surface of the zinc oxide, so that the surface energy of the obtained nano zinc oxide particles is reduced, and the problem of agglomeration of the nano zinc oxide is solved; because the surface is modified with a certain number of organic groups, the obtained nano zinc oxide can be well dispersed in common organic solvents; on the other hand, the modified carbon chain is very short and the hydrophobicity is not strong, so the obtained nano zinc oxide can still be dispersed in water. The double dispersion and non-agglomeration characteristics of the nano zinc oxide obtained by the method can be attributed to the modification of surface organic groups.
The nano zinc oxide prepared by the preparation method provided by the invention has no agglomeration, has double dispersion characteristics, can be well dispersed in water, monohydric alcohol and polyhydric alcohol which contain 1-10 carbon atoms such as ethanol, propanol, butanol, pentanol, hexanol, octanol and ethylene glycol, and organic solvents such as cyclohexane, normal hexane, carbon tetrachloride and petroleum ether, is white in color, and is easy to form a film (as shown in figure 2). The whole operation process of the method is simple and easy (as shown in figure 3).
Compared with the prior art. The invention has the advantages that:
1. the prepared zinc oxide nano-particles have double dispersion characteristics, can be dispersed in water, and can also be dispersed in aliphatic monohydric alcohol and polyhydric alcohol such as ethanol, glycol, glycerol, n-butanol, n-octanol and isooctanol, and common organic solvents such as cyclohexane, n-hexane, carbon tetrachloride and petroleum ether;
2. the esterification reaction speed is moderate, and the nano zinc oxide can be uniformly separated out, so that the obtained particle size distributionis narrow; is not easy to agglomerate; has good film forming property;
3. high-temperature calcination is not needed, and the required energy consumption is low; the product is white in chroma;
4. the reaction process does not need to adjust the pH value, and compared with the hydrothermal method in the prior art, the post-treatment is simple;
5. the filtrate can be used as a solvent for reaction for recycling for multiple times, and finally, the acetate of the fatty alcohol and the corresponding fatty alcohol can be obtained by fractionation and recovery, so that a zero-emission green process for producing the nano zinc oxide is expected to be realized;
6. simple process and equipment, low cost and easy industrial popularization.
Drawings
FIG. 1 is a TEM (transmission electron microscope) image of zinc oxide nanoparticles prepared by the present invention;
FIG. 2 is an SEM (scanning electron microscope) image of a nano-zinc oxide deposition film prepared by the invention;
FIG. 3 is a schematic process flow diagram of the preparation method of the present invention.
Detailed Description
Example 1.
Methanol and zinc acetate are put into an autoclave according to the ratio of 5: 1(mL/g) with the filling amount of 60 percent, and the autoclave is put into an oven after being screwed up and reacts for 2 hours at 200 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washingand drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 30 nm.
Example 2.
2 v% aqueous methanol (volume ratio methanol: water 1: 50) and zinc acetate 50: 1(mL/g) were placed in an autoclave at a fill level of 60%, screwed, placed in an oven, and reacted at 200 ℃ for 4 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 40 nm.
Example 3.
Ethanol and zinc acetate are put into an autoclave according to the ratio of 10: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 24 hours at 100 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 40 nm.
Example 4.
50 v% ethanol in water (volume ratio ethanol: water 1: 1) and zinc acetate in a ratio of 20: 1(mL/g) were placed in an autoclave at a fill level of 60%, screwed, placed in an oven, and reacted at 110 ℃ for 8 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 45 nm.
Example 5.
The filtrate of example 3 and zinc acetate were charged at a rate of 30: 1(mL/g) into an autoclave at a charge of 60%, and after screwing, the autoclave was placed in an oven and reacted at 80 ℃ for 36 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 50 nm.
Example 6.
The filtrate of example 4 was mixed with ethanol at a volume ratio of 1: 10, and then placed in an autoclave with zinc acetate at a volume ratio of 50: 1(mL/g) at a packing level of 60%, and after screwing, the autoclave was placed in an oven and allowed to react at 160 ℃ for 12 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 40 nm.
Example 7.
The ethylene glycol and the zinc acetate are put into an autoclave according to the ratio of 30: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 48 hours at 120 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 50 nm.
Example 8.
The normal propyl alcohol and the zinc acetate are put into an autoclave according to the ratio of 40: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 14 hours at 130 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 60 nm.
Example 9.
The filtrate of example 8 was mixed with ethanol at a volume ratio of 3: 2, and then charged into an autoclave with a charge of 60% together with zinc acetate at a ratio of 50: 1(mL/g), and the mixture was placed into an oven after screwing and reacted at 160 ℃ for 24 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 40 nm.
Example 10.
The normal propyl alcohol and the zinc acetate are put into an autoclave according to the ratio of 40: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 18 hours at 140 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 45 nm.
Example 11.
Isopropanol and zinc acetate are put into an autoclave according to the ratio of 10: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 20 hours at 150 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 60 nm.
Example 12.
Propylene glycol and zinc acetate were placed in an autoclave at a ratio of 20: 1(mL/g) at a loading of 60%, and after screwing, the autoclave was placed in an oven and allowed to react at 170 ℃ for 24 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 100 nm.
Example 13.
Glycerol and zinc acetate are put into an autoclave according to the ratio of 30: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 18 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 70 nm.
Example 14.
The n-butanol and zinc acetate were placed in an autoclave at a ratio of 8: 1(mL/g) at a loading of 60%, and after screwing, the autoclave was placed in an oven and allowed to react at 160 ℃ for 15 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 60 nm.
Example 15.
The sec-butyl alcohol and the zinc acetate are put into an autoclave according to the ratio of 25: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 36 hours at 150 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 80 nm.
Example 16.
The isobutanol and the zinc acetate are put into an autoclave according to the ratio of 8: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 48 hours at 130 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 60 nm.
Example 17.
Tert-butyl alcohol and zinc acetate are put into an autoclave according to the proportion of 12: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 12 hours at 200 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 70 nm.
Example 18.
1, 4 butanediol and zinc acetate are put into an autoclave according to the ratio of 20: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 48 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 80 nm.
Example 19.
N-pentanol and zinc acetate in the ratio of 15 to 1(mL/g) are filled in an autoclave with a filling amount of 60%, and the autoclave is put in an oven after being screwed and reacted for 20 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 50 nm.
Example 20.
T-amyl alcohol and zinc acetate are put into an autoclave according to the ratio of 20: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 24 hours at 200 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 70 nm.
Example 21.
Putting n-hexanol and zinc acetate into an autoclave according to the ratio of 10: 1(mL/g), wherein the filling amount is 60%, screwing, putting into an oven, and reacting for 36 hours at 160 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 70 nm.
Example 22.
2-hexanol and zinc acetate were placed in an autoclave at a ratio of 20: 1(mL/g) at a loading of 60%, screwed in and placed in an oven for reaction at 140 ℃ for 48 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 60 nm.
Example 23.
3-hexanol and zinc acetate were placed in an autoclave at a ratio of 10: 1(mL/g) at a loading of 60%, and after screwing, the autoclave was placed in an oven and allowed to react at 160 ℃ for 40 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing anddrying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 70 nm.
Example 24.
The n-heptanol and the zinc acetate are put into an autoclave according to the ratio of 20: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 36 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 80 nm.
Example 25.
N-octanol and zinc acetate were placed in an autoclave at a ratio of 15: 1(mL/g) with a fill of 60%, screwed, placed in an oven, and reacted at 200 ℃ for 24 hours. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 100 nm.
Example 26.
Isooctyl alcohol and zinc acetate are put into an autoclave according to the ratio of 25: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 30 hours at 180 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 100 nm.
Example 27.
The n-nonanol and the zinc acetate are put into an autoclave according to the ratio of 30: 1(mL/g), the filling amount is 60 percent, the autoclave is put into an oven after screwing, and the reaction is carried out for 36 hours at 250 ℃.After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 100 nm.
Example 28.
Placing n-decanol and zinc acetate into an autoclave according to a ratio of 50: 1(mL/g), wherein the filling amount is 60%, placing the autoclave into an oven after screwing, and reacting for 48 hours at 300 ℃. After the reaction is finished, naturally cooling to room temperature. And (4) removing the upper layer liquid, filtering, washing and drying the bottom precipitate to obtain the zinc oxide nano powder with the average particle size of 100 nm.
Claims (7)
1. A preparation method of nano zinc oxide comprises the following steps:
putting fatty alcohol or an aqueous solution thereof and zinc acetate into an autoclave according to the proportion of 5-50 ml: 1g, heating to 80-300 ℃, and reacting for 2-48 hours; after the reaction is finished, cooling to room temperature; filtering out the precipitate, and processing by conventional washing and drying processes to obtain the zinc oxide nano powder.
2. The method for preparing nano zinc oxide according to claim 1, wherein the aliphatic alcohol comprises monohydric alcohol, dihydric alcohol and polyhydric alcohol with carbon content of 1-10.
3. The method of claim 2, wherein the monohydric alcohol is methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, or decanol.
4. The method for preparing nano zinc oxide according to claim 2, wherein the dihydric alcohol is ethylene glycol, propylene glycol or butylene glycol.
5. The method for preparing nano zinc oxide according to claim 2, wherein the polyol is glycerol.
6. The method for preparing nano zinc oxide according to claim 1, wherein the volume ratio concentration of the fatty alcohol in the fatty alcohol aqueous solution is 2 to 99 v%.
7. The method for preparing nano zinc oxide according to claim 1, wherein the obtained filtrate or the mixed solution with ethanol is used as a solvent for the next reaction.
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| CN100500949C (en) * | 2005-08-30 | 2009-06-17 | 厦门大学 | Method for nano zinc oxide crystal surface controllable growth |
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