KR20150120616A - Manufacturing method of silica immobilized nano zinc oxide - Google Patents
Manufacturing method of silica immobilized nano zinc oxide Download PDFInfo
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- KR20150120616A KR20150120616A KR1020140046367A KR20140046367A KR20150120616A KR 20150120616 A KR20150120616 A KR 20150120616A KR 1020140046367 A KR1020140046367 A KR 1020140046367A KR 20140046367 A KR20140046367 A KR 20140046367A KR 20150120616 A KR20150120616 A KR 20150120616A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
Description
The present invention relates to a process for preparing a silica-nano-oxide complex, and more particularly, to a process for preparing zinc oxalate using a precursor of zinc dioxide, mixing the solution with a solution containing a silicon precursor, And more particularly to a method for producing a silica-nano-zinc oxide composite excellent in the dispersion characteristics of zinc.
As global pollution problems such as global warming are highlighted, regulations on CO 2 emissions of vehicles are strengthened, and countries around the world are enacting environmental regulation laws.
At this point where the seriousness of environmental pollution is emerging, studies are being carried out for measures against pollutants caused by automobiles. In the case of tires, the European Union, Japan, China, and the domestic market are subject to minimal regulation and at the same time, the tire labeling system is being voluntarily enforced. The tire efficiency rating system measures the rolling resistance and the wet road surface braking force of the tire products and displays them on the products by grading them. It is important for the consumers to select high-efficiency tires so that the tire which accounts for 4-7% To improve energy consumption efficiency and to reduce fuel consumption. With the introduction of this system, it is anticipated that the supply of high-efficiency tires, which is currently at a mild level, will become more active, which is expected to contribute greatly to the protection of the domestic environment.
Carbon black or silica is used as a reinforcing filler in rubber composite materials used in tire manufacturing.
Conventional reinforcing fillers are carbon black, natural rubber (NR), styrene-butadiene rubber (SBR), cis-1,4-polybutadiene (butadiene rubber ) ( cis- 1,4-polybutadiene (butadiene rubber)).
BACKGROUND ART [0002] In recent years, studies have been actively carried out to reduce the rotational resistance of a tire as a part of reducing environmental pollution caused by exhaust gas of an automobile. One of them is to use silica as a reinforcing filler instead of carbon black. The silica-rubber composite material can reduce the rolling resistance as well as the braking ability as compared with the carbon black-rubber composite material. For this reason, the use of silica as a reinforcing filler for composite materials for tire treads is increasing.
In general, vulcanization is carried out at the time of rubber synthesis in order to improve the tensile strength and abrasion resistance of rubber and to widen the temperature range in which elasticity can be maintained. In this portion, zinc oxide is used as an activator of vulcanization accelerator. However, heavy metals such as zinc oxide among tire pollution are left on the surface and around the road, and they penetrate into the soil, thereby polluting the ground water, leading to environmental pollution and destruction of ecosystem. In addition, silica was used as the rubber filler, and zinc oxide, which is a vulcanization accelerator, was separately mixed therewith, resulting in an increase in processing steps and a relatively high cost and time. In addition, zinc oxide was added in a relatively large amount in the range of several to several tens of micro (m), and the process cost was high.
Therefore, development is urgently needed to reduce the amount of zinc oxide used to mitigate the occurrence of zinc oxide in tires.
Accordingly, the inventors of the present invention have repeatedly carried out experiments to overcome the above-mentioned problems and used silica as a reinforcing filler in order to manufacture rubber suitable for tire labeling standard. In order to reduce the process cost and environmental pollution, Zinc oxide nanotubes were chosen to maintain the existing properties even if the amount used was reduced to 1/2. In order to solve the problem of agglomeration of zinc oxide with each other and disperse physically and chemically on silica, zinc oxalate, which is an intermediate material in the synthesis of zinc oxide, is mixed with silica to produce a composite material.
A problem to be solved by the present invention is to provide a process for producing a silica-nano-zinc oxide composite which can reduce the process cost and time, reduce the content of zinc oxide through nanoporation of zinc oxide, Method.
The present invention relates to a method for forming a zinc precursor, comprising the steps of: adding a zinc precursor to a solvent to form a zinc precursor solution; mixing the zinc precursor solution and an oxalic acid solution to form zinc oxalate; forming a mixed solution of a silicon precursor and ammonia Mixing and drying the mixed solution and the zinc oxalate, and sintering the dried product to obtain a silica-nano-zinc oxide complex in which the zinc oxide is dispersed in the silica matrix, And a method for producing a zinc oxide complex.
The zinc precursor may comprise zinc acetate.
The silicon precursor may include at least one material selected from the group consisting of tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS).
It is preferable that the zinc precursor solution and the oxalic acid solution are mixed so that the zinc precursor and the oxalic acid have a molar ratio of 0.3 to 1.2: 1.
The zinc oxalate preferably has a pH of 1.5 to 2.5.
The mixture of the mixed solution and the zinc oxalate preferably has a molar ratio of the zinc oxalate to the silicon precursor of 0.1 to 0.6: 1.
Preferably, the sintering is performed at a temperature of 415 DEG C to 600 DEG C at which the zinc oxalate is oxidized to zinc oxide.
The forming the mixed solution in which the silicon precursor and ammonia are mixed may include heating the mixed solution to a temperature of 40 to 95 캜.
The pH of the mixed solution is preferably 7 to 13.
The zinc precursor is added to the solvent and maintained at a temperature of 50 to 80 ° C to form the zinc precursor solution, and the solvent may include alcohols.
Silica was used as the rubber filler, and zinc oxide, which is a vulcanization accelerator, was separately mixed therewith, resulting in an increase in processing steps and a relatively high cost and time. In addition, zinc oxide was added in a relatively large amount in the range of several to several tens of micro (m), and the process cost was high.
In comparison with this, according to the present invention, the cost and time are reduced due to the reduction of the process steps, and the nano-size of the zinc oxide can be reduced to 1/2 of the amount of the existing zinc oxide, so that the process cost can be reduced. In addition, since the amount of zinc oxide is reduced and silica, which is a filler, and nano-zinc oxide are composited, it is possible to reduce pollutants generated when they are applied to a tire.
1 is a view showing an X-ray diffraction (XRD) pattern of zinc oxalate prepared according to Experimental Example.
FIG. 2 is a view showing a TGA (Thermogravimetric Analyzer) analysis result of zinc oxalate prepared according to Experimental Example.
FIG. 3 is a view showing an X-ray diffraction (XRD) pattern of the silica-nano-oxide zinc complex produced according to the experimental example.
FIG. 4 and FIG. 5 are transmission electron microscope (TEM) photographs of the silica-nano-zinc oxide composite prepared according to the experimental example.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.
The term "nano" refers to a size of 1 to 1,000 nm as a unit of nanometer (nm), and the term "nano zinc oxide" refers to zinc oxide (ZnO) having a particle size of 1 to 1,000 nm, As used herein.
The present invention provides a method for producing a silica-nano-oxide zinc complex. According to the present invention, it is possible to reduce the process cost and time, reduce the content of zinc oxide through the nano-formation of zinc oxide, and obtain a silica-nano-oxide zinc complex having excellent dispersion characteristics of the nano-zinc oxide in silica. The silica-nano zinc oxide composite can be applied as an eco-tire filler.
The method for preparing a silica-nano-oxide composite according to a preferred embodiment of the present invention includes the steps of forming a zinc precursor solution by adding a zinc precursor to a solvent, mixing the zinc precursor solution with an oxalic acid solution to form zinc oxalate A step of forming a mixed solution in which a silicon precursor and ammonia are mixed, mixing and drying the mixed solution and the zinc oxalate, and sintering the dried product to obtain a silica matrix - < / RTI > nano zinc oxide complexes.
Hereinafter, a method for producing a silica-nano-oxide zinc oxide composite according to a preferred embodiment of the present invention will be described in more detail.
A zinc precursor is added to the first solvent to form a zinc precursor solution. The zinc precursor may be zinc acetate. The first solvent is not particularly limited as long as it can dissolve the zinc precursor, but alcohols such as ethanol and methanol are preferably used. The temperature for dissolving the zinc precursor in the first solvent is about room temperature to about 80 ° C, preferably about 50 to about 80 ° C, and the dissolution is preferably performed for about 1 minute to about 48 hours.
Oxalic acid is added to the second solvent to form a oxalic acid solution. The second solvent is not particularly limited so long as it can dissolve oxalic acid, but alcohols such as ethanol and methanol are preferably used. The temperature for dissolving oxalic acid is not particularly limited, but oxalic acid is dissolved at a temperature of about room temperature to about 80 캜, preferably about 50 to 80 캜, in order to reduce the temperature difference when mixing with the zinc precursor solution.
The zinc precursor solution and the oxalic acid solution are mixed to form zinc oxalate as an intermediate. The mixing is preferably performed by dropping an oxalic acid solution into the zinc precursor solution. The zinc oxalate preferably has a pH of about 1.5 to 2.5. It is preferable that the zinc precursor solution and the oxalic acid solution are mixed so that the zinc precursor and the oxalic acid have a molar ratio of 0.3 to 1.2: 1. When the ratio of zinc precursor to oxalic acid is lowered, the particle shape changes from spherical to rod-shaped.
A mixed solution of a silicon precursor and ammonia is formed. The method of forming the mixed solution will be described in detail.
A silicon precursor is added to the third solvent to form a silicon precursor solution. The silicon precursor may be at least one material selected from the group consisting of tetraethyl orthosilicate (TEOS) and tetramethyl orthosilicate (TMOS). The third solvent is not particularly limited so long as it can dissolve the silicon precursor, but alcohols such as ethanol and methanol are preferably used. The temperature at which the silicon precursor is dissolved is not particularly limited. For example, the silicon precursor is dissolved at about room temperature to about 40 ° C.
Ammonia is added to the fourth solvent to form an ammonia solution. The fourth solvent is not particularly limited so long as it can dissolve ammonia, but alcohols such as ethanol and methanol are preferably used. The temperature at which ammonia is dissolved is not particularly limited. For example, ammonia is dissolved at about room temperature to about 40 ° C.
The silicon precursor solution and the ammonia solution are mixed to form a mixed solution. The mixed solution is preferably heated while being refluxed at a temperature of about 40 to 95 캜 for 1 minute to 24 hours. It is preferable that the silicon precursor solution and the ammonia solution are mixed so that the pH of the mixed solution becomes 7-13. Preferably, the silicon precursor solution and the ammonia solution are mixed at a ratio of 1M of ammonia to 1M of the silicon precursor to 0.2 mol of the silicon precursor.
The mixed solution and the zinc oxalate are mixed and dried. The mixing is preferably a batch mixing. The mixture of the mixed solution and the zinc oxalate preferably has a molar ratio of the zinc oxalate to the silicon precursor of 0.1 to 0.6: 1. The drying is preferably performed at a temperature of about 60 to 95 DEG C for 1 to 48 hours.
The dried product is sintered to obtain a silica-nano-zinc oxide complex in which the nanocrystalline zinc is dispersed in the silica matrix. Preferably, the sintering is performed at a temperature of 415 DEG C to 600 DEG C at which the zinc oxalate is oxidized to zinc oxide.
Hereinafter, the sintering process will be described in more detail.
The dried product is charged into a furnace such as an electric furnace, and a sintering process is performed. It is preferable that the sintering process is performed at a temperature of about 415 to 600 DEG C, which is a temperature at which the zinc oxalate is oxidized to zinc oxide, for about 1 to 48 hours. It is desirable to keep the pressure inside the furnace constant during sintering.
The sintering is preferably performed at a temperature of about 415 to 600 ° C. When the sintering temperature is lower than 415 ° C, the zinc oxalate may not be oxidized to zinc oxide. If the sintering temperature is higher than 600 ° C, the energy consumption may be excessive, which may be uneconomical.
The sintering temperature is preferably raised at a heating rate of 1 to 50 ° C / min. If the heating rate is too slow, it takes a long time to decrease the productivity. If the heating rate is too high, thermal stress is applied due to a rapid temperature rise It is preferable to raise the temperature at the temperature raising rate in the above range.
The sintering is preferably performed at a sintering temperature for 1 to 48 hours. If the sintering time is too long, the energy consumption is high, so it is not economical and further sintering effect can not be expected. If the sintering time is short, incomplete sintering can be achieved.
The sintering is preferably performed in an oxidizing atmosphere (for example, air or oxygen (O 2 ) atmosphere).
After the sintering process is performed, the furnace temperature is lowered to unload the silica-nano-zinc oxide composite. The furnace cooling may be effected by shutting down the furnace power source to cool it in a natural state, or optionally by setting a temperature decreasing rate (for example, 10 DEG C / min). It is preferable to keep the pressure inside the furnace constant even while the furnace temperature is lowered.
Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited to the following experimental examples.
6.585 g (0.03 mol) of zinc acetate, which is a zinc precursor, was added to 200 ml of ethanol, refluxed at 80 ° C for 30 minutes and stirred to form a zinc precursor (zinc acetate) solution, and 6.933 g (0.055 mol) And stirred at 60 < 0 > C for 30 minutes to form a solution of oxalic acid. The oxalic acid solution was dropped on the zinc acetate solution and mixed to form a white gel, which is zinc oxalate.
1 is a view showing an X-ray diffraction (XRD) pattern of zinc oxalate prepared according to Experimental Example.
FIG. 2 is a view showing a TGA (Thermogravimetric Analyzer) analysis result of zinc oxalate prepared according to Experimental Example.
Referring to FIG. 2, it was confirmed that the zinc oxalate was oxidized at a temperature of 415 DEG C or higher.
41.666 g (0.2 mole) of tetraethylorthosilicate as a silicon precursor was added to 126.74 ml of ethanol at room temperature to form a silicon precursor (tetraethylorthosilicate) solution, and 7.01 g of ammonia (total tetraethylorthosilicate Was dropwise added to 106.81 ml of ethanol at room temperature to dissolve the solution to form an ammonia solution. The ammonia solution was mixed batchwise into a tetraethyl orthosilicate solution to form a mixed solution. The mixed solution was heated while being refluxed at 80 DEG C for 6 hours.
The mixed solution and zinc oxalate were mixed in a batch manner and dried at 80 DEG C for 20 hours.
The dried product was sintered at 430 DEG C to obtain a silica-nano-zinc oxide composite.
FIG. 3 is a view showing an X-ray diffraction (XRD) pattern of the silica-nano-oxide zinc complex produced according to the experimental example.
Referring to FIG. 3, X-ray diffraction analysis of the prepared silica-nano-zinc oxide composite revealed two crystalline peaks of silica (SiO 2 ) and zinc oxide (ZnO).
FIG. 4 and FIG. 5 are transmission electron microscope (TEM) photographs of the silica-nano-zinc oxide composite prepared according to the experimental example.
Referring to FIGS. 4 and 5, it can be seen that the primary particle size of the silica-nano-zinc oxide composite is about 500 nm. It can be seen that the nanocrystalline zinc oxide has good dispersibility in silica.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.
Claims (10)
Mixing the zinc precursor solution and the oxalic acid solution to form zinc oxalate;
Forming a mixed solution in which a silicon precursor and ammonia are mixed;
Mixing and drying the mixed solution and the zinc oxalate; And
And sintering the dried product to obtain a silica-nano-zinc oxide composite in which the nanocrystalline zinc oxide is dispersed in the silica matrix.
And heating the mixed solution to a temperature of 40 to 95 占 폚.
Wherein the solvent comprises alcohols. ≪ RTI ID = 0.0 > 11. < / RTI >
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190046605A (en) * | 2017-10-25 | 2019-05-07 | 울산대학교 산학협력단 | Composite based melamine resin, and oil-water separating materials |
| CN115057466A (en) * | 2022-08-04 | 2022-09-16 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
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| TWI292322B (en) | 2000-09-25 | 2008-01-11 | Shiseido Co Ltd | Metal oxide/silica complex and cosmetics containing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190046605A (en) * | 2017-10-25 | 2019-05-07 | 울산대학교 산학협력단 | Composite based melamine resin, and oil-water separating materials |
| CN115057466A (en) * | 2022-08-04 | 2022-09-16 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
| CN115057466B (en) * | 2022-08-04 | 2024-03-08 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
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