KR101349909B1 - Fabrication of mesoporous silica particle with insect repellent - Google Patents

Abstract

The present invention relates to a method for manufacturing insect repellent powder through an impregnation method, and more specifically, to a method for manufacturing insect repellent powder, wherein the method manufactures insect repellent powder with uniform particle size distribution, minute particle size, and thermal stability by using an impregnation method and optimally controlling the impregnation amount of an insect repellent, mixing temperatures, mixing speeds, drying, and crushing, wherein the impregnation method dissolves the insect repellent in alcohol and puts the dissolved insect repellent into AEROSIL@200.

Description

Manufacturing method of insect repellent material powder by impregnation method {Fabrication of mesoporous silica particle with insect repellent}

 The present invention relates to a method of manufacturing the insect repellent material powder by the impregnation method, and more specifically, the impregnation amount of the repellent in the above process by using the impregnation method in which the insect repellent repellent is directly dissolved in alcohol and added to AEROSIL @ 200. By controlling the stirring speed, drying and grinding optimally, the present invention relates to a method for producing an insect repellent material powder having a uniform particle size distribution, fine particle size and thermal stability.

Global warming and humidification due to rapidly changing climate change is increasing the activity time and breeding activity of pests, and also increasing the number of insect openings, and increasing the possibility of incorporation of animal foreign materials during food manufacturing and distribution. . Recently, larvae of pests have been found in foodstuffs, and an increasing number of cases are offensive to consumers.

Pests that cause damage to these stored foods are called stored pests. These stored pests have strong cold resistance and are distributed throughout the world, including Korea, Japan, the United States, and Europe, and can be grown except in winter. However, due to the current global warming, as the average temperature of the earth has risen over the past 100 years, there has been a problem in that the time for breeding and storage of pests is increased.

Therefore, the problems of food stability due to the inflow of pests of food packaging are frequently generated and spread, and the insecticide method of food packaging is very poor against the invasion of pests in the storage and distribution process, so it is very necessary to secure safety.

Fumed silica, well known under the trade name AEROSIL @ 200 (Evonik Industry), is a silica particle produced under high temperature conditions and is known to have a relatively high specific surface area among commercially produced silica particles. Silicon tetrachloride is prepared by vaporization under hydrogen and oxygen conditions at high temperature, and the form of amorphous silica nanoparticles is associated with each other to form a pore structure. AEROSIL @ 200 is currently used commercially in a variety of industries, including toners, paints and sealants.

The inventors of the present invention, while researching an effective insect repellent method of food packaging, by controlling the amount of ethanol repellent material, the temperature in the reactor, the stirring speed, the conditions by the stirring time, drying, calcination, etc. to AEROSIL @ 200 Insect repellent material powder was impregnated with insect repellent. Through this, the present invention was completed by confirming that the production cost can be lowered by not using expensive equipment and that the insecticide powder having thermal stability can be obtained through optimization of the production process.

It is an object of the present invention to provide a method for preparing an insect repellent material powder comprising the step of dissolving the insect repellent repellent in alcohol, impregnating the dissolved insect repellent repellent in the fumed silica, and drying, calcining and pulverizing at appropriate conditions.

It is also an object of the present invention to provide an insect repellent material powder having a fine particle size and thermal stability prepared by the above method.

In order to solve the above problems, the present invention comprises the steps of 1) dissolving the insect repellent in alcohol, 2) mixing fumed silica in the mixture of step 1, impregnating the insect repellent in the fumed silica, 3) It provides a method for producing an insect repellent material powder comprising the step of drying the impregnation of step 2), 4) calcining the dry matter of step 3), and 5) crushing the calcined product of step 4) do.

Step 1) is a step of dissolving the insect repellent in alcohol. The insect repellent repellent is dissolved in alcohol to ensure proper dispersion of the insect repellent, and the insect repellent repellent is prepared in the liquid form so that the insect repellent may be impregnated in the fumed silica. This dissolution process facilitates the impregnation of the insect repellent in the fumed silica.

In this case, the alcohol used may be ethanol, methanol, propanol or butanol, but is not limited thereto. In one embodiment of the present invention, ethanol was used.

The term 'insect repellent' used in the present invention is a drug used for the purpose of chasing pests. Insect repellents differ from insecticides in that they do not actively kill pests.

In addition, the term "insect repellent material powder" used in the present invention means a powder impregnated with the fumed silica in the liquid repellent repellent.

In the present invention, the insect repellent repellent used in step 1) is not limited to anetol, cinnamic aldehyde or a mixture thereof.

In step 1), the mass ratio of the insect repellent avoidant and the alcohol is preferably 1: 5 to 1: 8. When the mass ratio of the insect repellent to the alcohol is less than 1: 5, there is a problem that the amount of alcohol is insufficient to impregnate the bulky fumed silica well. In addition, when the mass ratio of the insect repellent and alcohol exceeds 1: 8, the content of the insect repellent is relatively low, there is a problem that does not secure sufficient insect repellent performance.

Step 2) is a step of mixing the fumed silica (fumed silica) in the mixture of step 1, impregnated insect repellent in the fumed silica.

As used herein, the term fumed silica refers to very fine, less than 1 μm amorphous silica SiO ₂ produced by oxidation of silicon containing compounds. For example, fumed silica can be produced by steam phase hydrolysis of a chlorosilane, such as silicon tetrachloride, in a hydrogen / oxygen flame, with the following reaction scheme.

SiCl ₄ + H ₂ + O ₄ ------> SiO ₂ + HCl

In general, silica is manufactured by firing after calcination, whereas fumed silica is prepared by heating a conventional silica and then boiling it under a high temperature and vacuum to deposit it on a cold surface. Such fumed silica is more expensive than ordinary silica, but has the advantage of superior purity.

In the present invention, the fumed silica used in step 2) may be Aerosil @ 200, but is not limited thereto. Aerosil @ 200 is a trade name for fumed silica manufactured and sold by evonik industries. Specifically, Aerosil @ 200 is a hydrophobic fumed silica having a surface area of 200 m ² / g.

Before mixing the fumed silica and the insect repellent in the alcohol in step 2), the fumed silica may be subjected to a step of purifying to high temperature. At this time, the purification temperature is preferably 100 ℃ to 120 ℃. The purification process removes moisture present in the fumed silica having hygroscopicity.

By the mixing of step 2), fumed silica is impregnated with insect repellent dissolved in alcohol. At this time, the mixture of the mixture of step 1) and the fumed silica may be made by stirring at 60 ℃ to 80 ℃ for 6 hours to 8 hours. At this time, the stirring may be performed in the stirrer, but is not limited thereto.

Step 3) is a step of drying the fumed silica impregnated with the insect repellent. Through the drying process, all of the alcohol and water used as the solvent is removed. In this case, the drying may be performed at 80 ° C. to 120 ° C. for 8 hours to 24 hours. In particular, it may preferably be carried out at 100 ℃ for 12 hours. The drying may be performed in an oven, but is not limited thereto.

Step 4) is calcining the dried solid product. As used herein, the term 'calcination' refers to an operation of heating a substance to a high temperature to remove some or all of its volatile components. Through the calcination process of step 4), impurities remaining in the insecticide material powder are removed.

The calcination of step 4) may be performed at 100 ° C. to 150 ° C. for 2 hours to 10 hours. Preferably, it may be carried out at 120 ℃ for 6 hours. The calcination may be performed in an electric furnace, but is not limited thereto.

Step 5) above is to disintegrate the calcined solid product. As used herein, the term 'disintegration' refers to processing operations such as dispersing, micronizing, and unwinding fibrous materials with a relatively weak force. Through the disintegration of step 5), the aggregated portions may be separated from each other, thereby obtaining an insect repellent material powder.

Disintegration of step 5) may be performed by injecting air at an air pressure of 4 kgf to 8 kgf. Preferably, it may be carried out by blowing air at an air pressure of 6 kgf.

In the present invention, the insect repellent repellent was dissolved in ethanol, impregnated directly into AEROSIL @ 200 and dried to prepare an insect repellent material powder. Materials used in one embodiment of the present invention were insect repellent (mixture), ethanol (purity 99.99%) and Aerosil @ 200. Insect repellent powder material was finally prepared by varying the stirring speed, the amount of ethanol, the amount of repellent repellent, the stirring temperature, the stirring time, and the amount of AEROSIL @ 200. As a result, it was found that the amount of the insect repellent, the stirring time and the stirring temperature were the main factors affecting the impregnation amount, stability, particle size, and surface area of the finally prepared insect repellent powder.

In particular, in the present invention, by controlling the amount of the insect repellent repellent of the stirring process, the stirring time, the stirring temperature, the amount of AEROSIL @ 200 as described above, it is possible to obtain a cheap insect repellent powder having a fine particle size of about 20nm by the impregnation method. there was.

In addition, the insect repellent material powder produced by the impregnation method can be applied to various materials by freely controlling the amount of impregnation.

The present invention provides a method of simply preparing the insect repellent material powder without using expensive equipment by using an impregnation method of directly injecting a liquid insect repellent material dissolved in fumed silica. In particular, by controlling the amount of repellent repellent, the stirring time, the stirring temperature, the amount of fumed silica, drying and grinding, it is possible to produce a cheap insect repellent powder by the impregnation method, has a fine particle size and thermal stability Eggplant has the effect of providing insect repellent material powder.

1 is a photograph (Fig. 1a) and TEM image of the insect repellent material powder prepared according to the method of the present invention. (Fig. 1b: Aerosil @ 200, Figure 1c: 10% impregnated Aerosil @ 200 + insect repellent, Fig. 1d) : Aerosil @ 200 + insect repellent 20% impregnation, Figure 1e: Aerosil @ 200 + insect repellent 30% impregnation, Figure 1f: Aerosil @ 200 + insect repellent 40% impregnation, Figure 1g: Aerosil @ 200 + insect repellent 50% impregnation)
Figure 2 is a thermogravimetric analysis (TGA) results of the insect repellent repellent used in the present invention.
Figure 3 is a graph showing the specific surface area (Fig. 3a) and pore volume (Fig. 3b) of the insect repellent material powder according to the insect repellent impregnated amount
Figure 4 is a graph of thermogravimetric analysis of the insect repellent release behavior of the insect repellent material powder prepared according to the production method of the present invention.
5 is a graph analyzing loading contents according to the amount of impregnation in insect repellents.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

Example  1-9: Preparation of Insect Repellent Material Powder

As shown in Table 1, in the stirring step, the insect repellent material powder was prepared by varying the amount of insect repellent, AEROSIL @ 200, the amount of ethanol, the stirring temperature and the stirring time. For the production of insect repellent material powder, 99.99% ethanol and AEROSIL @ 200 purified at a temperature of 100 ° C. and insect repellent repellent were used. The components of repellent repellent were cinnamic aldehyde 2.5%, anetol 2.5%, and ethanol 47.5%. 47.5% of distilled water was mixed and used.

number
Stirring conditions Insect repellent AEROSIL @ 200 ethanol Stirring temperature Stirring time One 1 kg 6 kg 5 kg 60 ° C 3 hours 2 1 kg 7 kg 6 kg 60 ° C 3 hours 3 1 kg 9 kg 8 kg 60 ° C 3 hours 4 2 kg 6 kg 5 kg 70 ℃ 6 hours 5 2 kg 7 kg 6 kg 70 ℃ 6 hours 6 2 kg 9 kg 8 kg 70 ℃ 6 hours 7 3 kg 6 kg 5 kg 80 ℃ 8 hours 8 3 kg 7 kg 6 kg 80 ℃ 8 hours 9 3 kg 9 kg 8 kg 80 ℃ 8 hours

Specifically, the ash reactor for the insect repellent material was used 200L grade, ethanol was dissolved in the reactor containing the insect repellent repellent. Then, AEROSIL @ 200 purified at high temperature was added at a constant rate, and the insect repellent repellent dissolved in ethanol was impregnated into AEROSIL @ 200. At this time, the insect repellent repellent and AEROSIL @ 200 dissolved in ethanol was impregnated with the insect repellent while stirring at 300 rpm through a stirrer. At this time, the stirring temperature was adjusted to a temperature range of 60 ℃ to 80 ℃, the stirring time was changed to 3 hours, 6 hours, 8 hours respectively.

The liquid insect repellent material obtained in the dissolving and stirring step was then dried at 100 ° C. for 12 hours using a drying oven in the drying step to evaporate both ethanol and water used for stirring. After drying, the physically aggregated large mass was pulverized with a pestle and passed through 200 mesh, followed by calcination for 6 hours at 120 ° C. in an electric furnace to remove remaining impurities in the product. Thereafter, by spraying a high pressure air of 6 kgf pneumatic pressure to the insect repellent material powder was pulverized so that the aggregated parts between the particles can be separated from each other to prepare a insect repellent material powder.

Experimental Example  1: Investigation of particle shape and size of insect repellent material powder

For the insect repellent material powder obtained in the above example, the crystal structure, particle size and shape of the particles were analyzed using Electron Microscope (TEM). The results are shown in Fig.

Figure 1a is a 20 nm size of the yellowish brown insect repellent material powder obtained in the present invention, Figure 1b is a TEM image (sclae bar: 100 nm). Through this, it was possible to confirm the color and crystal structure of the prepared insect repellent material powder.

Experimental Example  2: Insect repellent  Thermal Stability Analysis

In order to investigate the thermal stability of the insect repellent used in the present invention, a thermogravimetric analysis was performed. To this end, a certain amount of Nano fabrication was put into a platinum sample pan, and heated up to 800 ° C. using nitrogen gas at a flow rate of 20 ml / min at 100 ° C. The weight change with temperature increase is shown in FIG.

As a result, it showed a residual amount of more than 90% at a temperature of 200 ℃, even after raising the temperature to 800 ℃ showed a residual amount of more than 70%. This confirmed that the insect repellent was thermally stable.

Experimental Example  3: insect repellent On impregnation  Analysis of Insect Repellent Material Powder

In order to determine the impregnation amount of each prepared insect repellent powder, a thermogravimetric analysis was performed. To this end, a certain amount of nano fabrication was put into a platinum sample pan, and the temperature was raised to 800 ° C. using nitrogen gas at a flow rate of 20 ml / min at 100 ° C. The same experiment was repeated five times to confirm the error range, and the minimum value of the data was selected as the data. The impregnation amount was determined by the method described above, and an insecticide material powder having an impregnation amount of 10%, 20%, 30%, 40%, and 50% was prepared. Each powder was named KP 1 (10%), KP 2 (20%), KP 3 (30%), KP 4 (40%), KP 5 (50%) depending on the amount of impregnation.

The specific surface area (FIG. 3a) and pore volume (FIG. 3b) of the insect repellent material powder according to the impregnation amount are shown in FIG. 5. The specific surface area and pore volume change of the insect repellent material powder according to the impregnation amount are shown in Table 2 below.

Sample name Surface area Pore volume Aerosil 170.0 m ² / g 0.429 cm ³ / g KP 1 124.9 m ² / g 0.630 cm ³ / g KP 2 95.4 m ² / g 0.550 cm ³ / g KP 3 73.2 m ² / g 0.440 cm ³ / g KP 4 57.1 m ² / g 0.390 cm ³ / g KP 5 28.5 m ² / g 0.267 cm ³ / g

As shown in the above table, when the insect repellent is impregnated with Aerosil, the pores of Aerosil @ 200 were closed by the insect repellent, and thus the specific surface area and the pore size decreased as the impregnation amount increased. The pore volume was higher than that of Aerosil @ 200 for samples with a 10% to 30% impregnation volume, indicating that the pore volume decreases when the impregnating repellent impregnation amount is 30% or more.

Experimental Example  4: Analysis of Repellent Release Behavior of Insect Repellent Powder

The results of the release behavior of the insect repellent repellent of the prepared insect repellent material powder is shown in FIG. For emission behavior analysis, thermogravimetric analysis was performed using air gas at a flow rate of 20 ml / min at 100 ° C. The reduced weight was measured for 24 hours, and the residual amount confirmed at 5 hours, 15 hours, and 24 hours is shown in Table 3 below. The decrease at this time is the release amount of the insect repellent.

Sample name
Time (hr) Comparison
5 15 25 KP 1 96 wt% 96 wt% 96 wt% 4 wt% KP 2 96 wt% 96 wt% 96 wt% 4 wt% KP 3 95 wt% 95 wt% 94 wt% 6 wt% KP 4 93 wt% 92 wt% 92 wt% 8 wt% KP 5 92 wt% 91 wt% 91 wt% 9 wt%

As a result, the amount of KP 1 and KP 2 released for 24 hours was 4 wt%, KP 3 was 6 wt%, and KP 4 and KP 5 represented 8% and 9%, respectively, as shown in FIG. It was confirmed that the function of nano fabrication is maintained at a constant emission amount.

Experimental Example  5: avoid insect repellent On impregnation  Following Loading contents  Content analysis

The samples prepared at different impregnation amounts were heated to 800 ° C. to perform thermogravimetric analysis, and the results are shown in Table 4 and FIG. 5.

Sample name Repllent addition Loading contents KP 1 10 wt% 9 wt% KP 2 20 wt% 15 wt% KP 3 30 wt% 20 wt% KP 4 40 wt% 28 wt% KP 5 50 wt% 35 wt%

As a result, as the impregnation of the insect repellent repellent increased, it was confirmed that the content of the loading contents increased.

Claims (10)

1) dissolving the insect repellent in alcohol;
2) mixing fumed silica to the mixture of step 1, impregnating the insect repellent in the fumed silica;
3) drying the impregnation of step 2);
4) calcining the dried product of step 3), and
5) A method for preparing insect repellent material powder comprising the step of crushing the calcined product of step 4).
The method of claim 1, wherein the alcohol is ethanol, methanol, propanol or butanol.
The method of claim 1, wherein the insect repellent repellent is anetitol, cinnamic aldehyde or a mixture thereof.
The method of claim 1, wherein the mass ratio of the insect repellent repellent and the alcohol in step 1) is 1: 5 to 1: 8.
The method of claim 1, wherein the fumed silica of step 2) has a surface area of 200 m ² / g.
The method according to claim 1, wherein the mixing ratio of the material of step 1) and the fumed silica in step 2) is 10 to 50% by weight based on the fumed silica.
The method of claim 1, wherein the mixing of step 2) is performed by stirring at 60 ° C. to 80 ° C. for 6 hours to 8 hours.
The method of claim 1, wherein the drying of step 3) is performed at 80 ° C to 120 ° C for 8 to 24 hours.
The method according to claim 1, wherein the calcination in step 4) is performed at 100 ° C. to 150 ° C. for 2 hours to 10 hours.
The method of claim 1, wherein the disintegration of step 5) is performed by injecting air at an air pressure of 4 kg _f to 8 kg _f .

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