KR101028041B1 - Method for fabricating thermo-responsive micelle and method for treatment of toxic substance using thermo-responsive micelle - Google Patents

Abstract

The present invention relates to a temperature sensitive micelle, a method for manufacturing the same, and a method for treating harmful substances using a temperature sensitive micelle, which can effectively remove a small amount of harmful chemicals contained in sewage water, and according to the present invention, a temperature sensitive micelle The method for treating harmful substances using the temperature-sensitive micelle is composed of a core region and a cell region, the core region is composed of a hydrophobic polymer, the cell region is composed of an amphiphilic polymer, and the amphiphilic polymer is a solution. The solution is hydrophilic when the solution is higher than the critical solution temperature, hydrophobic when the solution is lower than the critical solution temperature, and when the amphiphilic polymer is hydrophilic, trapping is isolated from the outer space between the core region and the cell region Area is provided,

When the amphiphilic polymer is hydrophobic, the collection region is released, and (a) administering the temperature sensitive micelle in the wastewater containing the hazardous substance, and the temperature of the wastewater is greater than the critical solution temperature of the amphiphilic polymer. (B) allowing the hazardous substances to be collected in the collection region so as to be high, and filtering the temperature-sensitive micelles that collect the hazardous substances from the wastewater and administering the same to a separate reservoir. (D) discharging the harmful substances trapped in the micelles by lowering the temperature below the critical solution temperature, and (e) filtering the temperature sensitive micelles in the reservoir.

Micelles, temperature sensitive, BTEX

Description

Method for fabricating thermo-responsive micelle and method for treatment of toxic substance using thermo-responsive micelle}

The present invention relates to a temperature sensitive micelle, a method for manufacturing the same, and a method for treating harmful substances using a temperature sensitive micelle, and more particularly, a temperature sensitive micelle that can effectively remove a small amount of harmful chemicals contained in sewage water. And it relates to a manufacturing method and a method for treating harmful substances using a temperature sensitive micelle.

Due to the development of industry and urban concentration of population, the problem of water pollution is getting serious day by day. Due to the increase of human activity and industrial production, the large amount of nitrogen, phosphorus and organic matter contained in sewage and waste water are no longer caused by natural self-cleaning action. A situation was reached in which processing could not be relied on.

Biological nutrients such as nitrogen and phosphorus are essential nutrients for the growth of organisms, but when they are insufficiently treated, they cause eutrophication and exacerbate water pollution. Such biological nutrients may be prepared using biological sewage treatment methods such as continuous flow type A2 / O, VIP, MUCT, 5-stage Bardenpho, intermittent aeration, or sequencing batch reactors. Most are eliminated through.

Meanwhile, trace waste chemicals such as benzene, toluene, ethylbenzene, and xylene are present in the wastewater in addition to the biological nutrients such as nitrogen and phosphorus described above. The same trace chemicals are not removed through conventional biological sewage treatment. In addition, a technique of decomposing and purifying a small amount of organic matter remaining in the wastewater by using an inorganic oxide photocatalyst has been proposed, but also has a disadvantage in that carcinogenic substances such as benzene and toluene are not removed.

Currently, more than 36,000 chemicals are in circulation in Korea, and 200 new chemicals are entering the domestic market every year, and the amount and amount of harmful chemicals flowing into sewage water are bound to increase. Therefore, it is urgent to develop a technology that can effectively remove the harmful chemicals contained in such wastewater.

The present invention has been made to solve the above problems, a temperature-sensitive micelle and a method of manufacturing the same and a method for treating harmful substances using a temperature-sensitive micelle that can effectively remove the trace amount of harmful chemicals contained in the waste water. The purpose is to provide.

The temperature-sensitive micelle according to the present invention for achieving the above object consists of a core region and a cell region, the core region is composed of a hydrophobic polymer, the cell region is composed of an amphiphilic polymer, the amphiphilic polymer Is hydrophilic when the solution is above the critical solution temperature in the solution, hydrophobic when the solution is below the critical solution temperature, and is isolated from the outer space between the core region and the cell region when the amphiphilic polymer is hydrophilic. Characterized in that the collection area is provided.

The hydrophobic polymer of the core region may be polymethyl meta-acrylate (PMMA). The amphiphilic polymer of the cell region may be P (NIPAm) (Poly (N-isopropyl acrylamide)). The size of the collection region may be controlled by controlling the molecular weight of the hydrophobic polymer of the core region and the amphiphilic polymer of the cell region.

The method of manufacturing a temperature sensitive micelle according to the present invention comprises the steps of forming a polymer in the core region, forming a connection in the polymer of the core region and forming a polymer in the cell region in the connection portion It features.

The polymer of the core region may be made of PMMA, the polymer of the cell region may be made of P (NIPAm), and the PMMA may be formed through the reaction of a single molecule and an initiator. In addition, the molecular weight of the PMMA may be adjusted by adjusting the ratio of the single molecule and the initiator, and the molecular weight of the polymer of the cell region is proportional to the molecular weight of the polymer of the core region.

In the method for treating harmful substances using a temperature sensitive micelle according to the present invention, the temperature sensitive micelle comprises a core region and a cell region, the core region is composed of a hydrophobic polymer, and the cell region is composed of an amphiphilic polymer. The amphiphilic polymer is hydrophilic when the solution is higher than the critical solution temperature in the solution, hydrophobic when the solution is lower than the critical solution temperature, and the core region and the cell region when the amphiphilic polymer is hydrophilic. Between the outer space and the collection area is isolated,

When the amphiphilic polymer is hydrophobic, the collection region is released, and (a) administering the temperature sensitive micelle in the wastewater containing the hazardous substance, and the temperature of the wastewater is greater than the critical solution temperature of the amphiphilic polymer. (B) allowing the hazardous substances to be collected in the collection region so as to be high, and filtering the temperature-sensitive micelles that collect the hazardous substances from the wastewater and administering the same to a separate reservoir. (D) discharging the harmful substances trapped in the micelles by lowering the temperature below the critical solution temperature, and (e) filtering the temperature sensitive micelles in the reservoir.

The temperature sensitive micelle according to the present invention, a method for producing the same, and a method for treating harmful substances using the temperature sensitive micelle have the following effects.

As the hazardous substance is selectively collected and released according to the critical melting temperature, it is possible to effectively collect harmful chemicals such as benzene, and also to remove and recycle the collected harmful substances.

Hereinafter, a temperature sensitive micelle according to an embodiment of the present invention, a method for manufacturing the same, and a method for treating harmful substances using the temperature sensitive micelle will be described in detail with reference to the accompanying drawings.

First, a temperature sensitive micelle according to an embodiment of the present invention will be described. The temperature sensitive micelle according to an embodiment of the present invention is composed of a core region and a shell region, as shown in FIG. 1, wherein the core region is made of a hydrophobic polymer and the cell region is amphiphilic. It consists of a polymer.

As the hydrophobic polymer constituting the core region, polymethyl meta-acrylate (PMMA) may be used. The amphiphilic polymer constituting the cell region may be P (NIPAm) (Poly (N-isopropyl acrylamide)) or the like. Can be applied. In this case, the amphiphilic polymer refers to a polymer having both hydrophilicity and hydrophobicity. In the present invention, the amphiphilic polymer has hydrophilicity or hydrophobicity depending on temperature. In detail, the amphiphilic polymer has hydrophilicity above a critical solution temperature and hydrophobicity below a critical solution temperature. Here, the critical solution temperature is variable depending on the material constituting the amphiphilic polymer.

The cell region is arranged in the form of a branch around the core region. The cell region is shown in FIGS. 1A and 1B according to whether the amphiphilic polymer of the cell region is hydrophilic or hydrophobic. It has a star or circular shape as shown. Specifically, when the amphiphilic polymer in the cell region is hydrophilic, that is, when the temperature of the solution containing the micelle is higher than the critical solution temperature, the micelle has a circular shape (see FIG. 1A). On the contrary, when the amphiphilic polymer in the cell region is hydrophobic, that is, when the temperature of the solution is lower than the critical solution temperature, the micelle has a star shape (see FIG. 1B). In other words, if the temperature of the solution is higher than the critical solution temperature, the micelle has a circular shape, and if it is lower than the critical temperature, the micelle has a star shape.

In addition, the micelles have a circular shape, so that a substance having a predetermined molecular weight, for example, harmful chemicals such as benzene, toluene, ethylbenzene, and xylene may be collected. It means that it is provided in the space. Specifically, when the micelle has a circular shape, a predetermined space is provided between the core region and the cell region, and the space is defined as a collecting region. The collection region is in a state of being cut off from the external space by the cell region. On the contrary, the micelle shape means that the capture area is not defined, and no harmful chemicals or the like can be collected in this state.

The temperature sensitive micelle according to the embodiment of the present invention has been described above. Next, a method of manufacturing a temperature sensitive micelle according to an embodiment of the present invention will be described. The method of manufacturing a temperature sensitive micelle according to an embodiment of the present invention proceeds in the order of a core region forming step, a connecting portion forming step, and a cell region forming step. Figure 2 is a schematic diagram showing a method of manufacturing a temperature sensitive micelle according to an embodiment of the present invention.

First, the core region forming step is a step of forming a hydrophobic polymer forming a core region by reacting a single molecule with an initiator. For example, MMA (methyl meta-acrylate) may be used as the single molecule, 2-bromoisobutyryl bromide may be used as the initiator, and PMMA (polymethyl meta) as a hydrophobic polymer constituting the core region. -acrylate) can be formed. Here, PMMA having a plurality of branches may be formed according to the properties of the initiator. In the embodiment of the present invention, PMMA having four branches was formed.

In this case, the polymer size, that is, the molecular weight of the core region may be controlled by adjusting the ratio of the single molecule and the initiator. The reason for controlling the molecular weight of the polymer of the core region is to selectively control the size of the capture region existing between the core region and the cell region when the micelle forms a circular shape. This is because harmful polymers can be collected.

In the state in which the polymer in the core region is formed, a polymer forming a cell region must be formed in each branch of the core region. The forming step proceeds first.

The connecting part forming step is in detail in one embodiment of the present invention, 1) forming P (HEMA-TMS) in PMMA, and 2) PMMA-bP (HEMA-TMS) PMMA-bP (HEMA-IBB) The process of converting to.

1) The process of forming P (HEMA-TMS) on PMMA is specifically, mixing PMMA and P (HEMA-TMS), and then performing PMMA-bP (HEMA-TMS) through ATRP (Atomic transfer radical polymerization) reaction. It is a process of formation. Next, 2) the process of converting PMMA-bP (HEMA-TMS) to PMMA-bP (HEMA-IBB), PMMA-bP (HEMA-TMS) is mixed with KF / TBAF and 2-Br-IBB PMMA -bP (HEMA-IBB)

1) forming P (HEMA-TMS) on the PMMA, and 2) connecting parts to each branch of the core region through the process of converting PMMA-bP (HEMA-TMS) into PMMA-bP (HEMA-IBB). The formation of is completed.

In this way, the step of forming a polymer forming a cell region on each branch of the core region in the state where the connection portion is formed. Specifically, PMMA-b-P (HEMA-IBB) and NIPAm (N-isopropyl acrylamide) are mixed, and then ATRP reaction to form a polymer of the cell region consisting of P (NIPAm). At this time, the polymer of the cell region can control the molecular weight similarly to the polymer of the core region, and its purpose is to control the size of the capture region when the micelle forms a circular shape similarly to the polymer molecular weight control of the core region. To do this. Molecular weight control of the polymer in the cell region depends on molecular weight control of the core region. That is, when the molecular weight of the core region polymer is small, the molecular weight of the cell region polymer is also small, and when the molecular weight of the core region polymer is large, the molecular weight of the cell region polymer is also large.

Table 1 and Table 2 below show the molecular weight of the core region polymer and the cell region polymer, respectively. As shown in Table 1 and Table 2, it can be seen that the molecular weight of the core region polymer and the molecular weight of the cell region polymer have a proportional relationship. However, in the case of the core region polymer (PMMA), the probability of formation was relatively similar regardless of the size of the molecular weight, but in the case of the small molecular weight of the core region polymer (PMMA), the probability of formation of the cell region polymer (PNIPAM) was 14%, The 15k PMMA is 25%).

Table 1 PMMA Molecular Weight and Probability

Core Area Polymer % Chance of creation Actual molecular weight (g / mol) 8k PMMA 75 7,880 15k PMMA 72 13,100

<Table 2> Molecular weight and production probability of PNIPAM according to the molecular weight of PMMA

Core Area Polymer % Chance of creation Actual molecular weight (g / mol) 8k PMMA 14 184,000 15k PMMA 25 439,200

In the above, the temperature-sensitive micelle according to an embodiment of the present invention and a manufacturing method thereof have been described. Finally, a method for treating harmful substances using a temperature sensitive micelle according to an embodiment of the present invention will be described. Figure 3 is a flow chart for explaining a hazardous material treatment method using a temperature sensitive micelle according to an embodiment of the present invention.

The temperature sensitive micelle used in the method for treating a hazardous substance according to an embodiment of the present invention has a temperature sensitive micelle structure as described above. That is, the polymer consisting of the core region and the cell region, and the polymer constituting the cell region is an amphiphilic polymer having hydrophilicity when the ambient temperature is higher than the critical solution temperature, and hydrophobic when the ambient temperature is lower than the critical solution temperature.

In using such a temperature sensitive micelle, the method for treating harmful substances according to an embodiment of the present invention is largely divided into a hazardous substance collecting step and a micelle regeneration step.

First, the step of capturing the hazardous substances, the micelles are administered in the wastewater containing traces of harmful substances such as benzene, toluene, ethylbenzene, and xylene (S301). (See FIG. 4A). If the temperature of the waste water is higher than the critical solution temperature of the amphiphilic polymer constituting the cell region of the micelles, the administered micelles form a circular shape, and a trapping region is formed between the core region and the cell region, and harmful substances in the collecting region. This is collected (S302) (S303) (see Fig. 4B). For reference, FIG. 5 is a photograph showing a process in which harmful substances are collected when a micelle to which amphiphilic polymer is applied having a critical solution temperature of about 20 ° C. has a temperature of 32 ° C.

On the other hand, when the temperature of the wastewater is lower than the critical solution temperature, the temperature of the wastewater is higher than the critical solution temperature so that the micelles have a circular shape, so that the hazardous substances are collected in the capture area.

In a state where harmful substances are collected in the micelles, the regeneration step of the micelles is performed. Specifically, the micelles collecting harmful substances are filtered from the wastewater and administered to a separate reservoir (S304). Subsequently, the temperature of the reservoir is lower than the critical solution temperature so that harmful substances collected in the micelle are discharged (S305) (S306). Then, filtering the micelles in the reservoir is completed (S307).

1 is a block diagram showing a temperature sensitive micelle according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing a method of manufacturing a temperature sensitive micelle according to an embodiment of the present invention.

Figure 3 is a flow chart for explaining a hazardous material treatment method using a temperature sensitive micelle according to an embodiment of the present invention.

Figure 4a is a reference diagram showing a state in which the temperature sensitive micelles are administered in the wastewater containing harmful substances.

Figure 4b is a reference diagram showing a state in which harmful substances collected in the waste water by the temperature sensitive micelle.

5 is a photograph showing the process of collecting harmful substances when the temperature of the solution is 32 ℃ micelle to which the amphiphilic polymer is applied, the critical solution temperature is about 20 ℃.

Claims (10)

delete delete delete delete Forming a polymer of the core region; Forming a connection portion in the polymer of the core region; And Method for producing a temperature-sensitive micelle comprising the step of forming a polymer of the cell region in the connecting portion. The method of claim 5, wherein the polymer of the core region is made of PMMA, and the polymer of the cell region is made of P (NIPAm). The method of claim 6, wherein the PMMA is formed by reacting a single molecule with an initiator. The method of claim 7, wherein the molecular weight of the PMMA is adjusted by adjusting the ratio of the single molecule and the initiator. The method of claim 5, wherein the molecular weight of the polymer of the cell region is proportional to the molecular weight of the polymer of the core region. In the method of treating harmful substances using a temperature sensitive micelle, The temperature sensitive micelle, It consists of a core region and a cell region, The core region is composed of a hydrophobic polymer, the cell region is composed of an amphiphilic polymer, the amphiphilic polymer is hydrophilic when the solution is higher than the critical solution temperature in the solution, when the solution is lower than the critical solution temperature Hydrophobic, When the amphiphilic polymer is hydrophilic, a trapping region is provided between the core region and the cell region and is separated from the outer space. When the amphiphilic polymer is hydrophobic, the trapping region is released. (A) administering the temperature sensitive micelles in the wastewater containing harmful substances; (B) increasing the temperature of the wastewater to be higher than the critical solution temperature of the amphiphilic polymer to collect harmful substances in the collection region; (C) filtering the temperature sensitive micelles collecting the harmful substances from the wastewater and administering them to a separate reservoir; (D) allowing the temperature of the reservoir to be lower than a critical solution temperature to discharge harmful substances collected in the micelle; And And (e) filtering out the temperature sensitive micelle in the water reservoir.

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