KR101639376B1 - Nanochannel polymer composite, preparing method of the same, and membrane including the same - Google Patents

Abstract

A nanocarbon polymer composite, a method for producing the nanocarbon polymer composite, and a membrane including the nanocarbon polymer composite.

Description

TECHNICAL FIELD [0001] The present invention relates to a nanocarbon polymer composite, a nanocarbon polymer composite, a method for producing the nanocarbon polymer composite, a membrane including the nanocarbon polymer composite,

The present invention relates to a nanochannel polymer composite, a method of making the nanochannel polymer composite, and a membrane comprising the nanochannel polymer composite.

A polymer membrane (polymer membrane or polymeric membrane) is a membrane in the form of a polymer interphase, capable of selectively transferring certain components or molecules to opposite sides. The polymer membrane can be used for various structures due to the transfer characteristics, and is mainly used for diffusion. In addition, the polymer membrane can be used as an application for separating a fluid, a gas or the like and delivering a specific component or molecule.

Conventional polymer membranes are liquefied and injected between channels to fill the polymer between the outer and inner walls of the channel. At this time, the polymer is liquefied with a solvent, and the solvent is evaporated by increasing the temperature to remove the solvents that dissolve the polymer, and the polymer is left in the evaporated place so that the polymer is filled in the desired place Respectively. However, as the thickness of the polymer increases, it takes a long time to evaporate the solvent, and bubbles are generated inside the polymer. The bubbles are defects inside the polymer and become a part of the leakage which is fatal in the formation of the membrane. In addition, the substances used as the solvent easily evaporate and are absorbed into the body through the respiratory organs. These solvents are highly toxic and can cause anesthesia and headache by causing harm to the brain and nerves. Therefore, there is a problem that safety must be taken care of during the process.

In microchannel devices such as biochips, membranes are very difficult to form and require precise work, but they are not easy to seal or fabricate, and the shape of membranes that can be fabricated is very limited. For example, closed loop shaped membranes have not yet been realized in reality due to difficulties in fabrication compared to their necessity.

On the other hand, Korean Patent Registration No. 10-0684989 discloses a semiconductor device including an insulating film formed on a substrate, an oxide base film patterned on the insulating film, and an oxide film formed on a sidewall of the oxide base film, wherein an empty space is formed between the insulating film and the oxide film And a method of forming the nanochannel.

One embodiment of the present invention is to provide a nanochannel polymer composite, a method of making the nanochannel polymer composite, and a membrane comprising the nanochannel polymer composite.

It should be understood, however, that the technical scope of the present invention is not limited to the above-described technical problems, and other technical problems may exist.

According to a first aspect of the present invention, there is provided a method for producing a thermoplastic polymer, comprising the steps of: heating a thermoplastic polymer at a temperature above the glass transition temperature of the thermoplastic polymer and below the melting point of the thermoplastic polymer; Immersing the nanotube material on the heated thermoplastic polymer; And cooling the thermoplastic polymer in which the nano channel material is immersed.

According to a second aspect of the present invention, there is provided a nanochannel polymer composite comprising a thermoplastic polymer prepared according to the manufacturing method of the first aspect of the present invention, wherein the nanochannel material is immersed.

A third aspect of the invention provides a membrane comprising a nanotube polymer composite according to the second aspect of the present invention.

According to one of the above-mentioned means for solving the problems, in the nanotube polymer composite according to one embodiment of the present invention, the method for producing the nanotube polymer composite, and the membrane comprising the nanotube polymer composite, A method of heating a thermoplastic polymer immersed in a nano channel substance using a method of heating the thermoplastic polymer at a temperature not lower than the glass transition temperature (Tg) of the thermoplastic polymer and not higher than the melting point without using a solvent, And environmentally friendly, and the process of melting the thermoplastic polymer in a solvent can also be reduced. Furthermore, since the solvent causes bubbles to form inside the thermoplastic polymer, the problem of leading to leakage does not occur. As a result, one embodiment of the present invention is able to form desired nanochannels within the thermoplastic polymer by an eco-friendly process method.

In addition, since the thermoplastic polymer can be recycled by its nature, the thermoplastic polymer used in the production of the nanotube polymer composite can be recycled, and waste of resources can be reduced.

FIGS. 1A and 1B are schematic views illustrating a manufacturing process of a nanotube polymer composite in one embodiment of the present invention. FIG.
FIG. 2A is a photograph of a polystyrene composite in which CNTs are immersed, FIG. 2B is a schematic diagram of a polystyrene composite in which CNTs are immersed in one embodiment of the invention, and FIGS. 2C-2F are cross- In one embodiment, it is an electron microscope image of the TOP, MID, and BOT portions of the CNT-immersed polystyrene complex.
FIG. 3A is an electron microscope image showing a cross section of a CNT-immersed polystyrene composite according to an embodiment of the present invention, and FIGS. 3B to 3D illustrate an example of the CNT-immersed polyethylene composite ), Middle (MID), and bottom (BOT) portions.
FIG. 4A is an electron microscope image of a cross section of a CNT-immersed polysulfone complex in one embodiment of the present invention, and FIGS. 4B-4D are cross-sectional views of an embodiment of the CNT- (TOP), middle (MID), and bottom (BOT) portions.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

According to a first aspect of the present invention, there is provided a method for producing a thermoplastic polymer, comprising: heating a thermoplastic polymer at a temperature equal to or higher than the glass transition temperature (Tg) of the thermoplastic polymer and equal to or lower than the melting point of the thermoplastic polymer; Immersing the nanotube material on the heated thermoplastic polymer; And cooling the thermoplastic polymer in which the nano channel material is immersed.

In one embodiment of the present invention, when the membrane is formed by forming a channel inside the polymer, a process of forming the channel without dissolving the polymer in the solvent is provided. Specifically, a conventional membrane manufacturing method is a method in which a polymer is dissolved by dissolving a polymer in a solvent to make the polymer flowable, and then the solvent is evaporated to leave only the polymer so as to wrap the outer portion of the channel with the polymer or to evaporate the solvent The resulting hole itself is used as a membrane. The solution in which the polymer melts to increase the fluidity of the solvent can easily fill the gap between the outer wall of the channel and the outer wall. However, the solvent for dissolving the polymer is harmful to the body and the environment, and the thicker the polymer is, the more the bubbles in the polymer can not escape when the solvent is evaporated. In one embodiment of the present invention, there is provided a nanochannel polymer that fills an outer wall and an outer wall of a channel using the characteristics of the thermoplastic polymer, without using a method of dissolving the polymer in a solvent, and a method of manufacturing the nanochannel polymer .

In this regard, FIGS. 1A and 1B are schematic views illustrating a manufacturing process of the nanotube polymer composite in one embodiment of the present invention.

In one embodiment of the invention, the nanotube material 10 is placed on the surface of the thermoplastic polymer 20 (FIG. 1A) and the thermoplastic polymer 20 is heated to a temperature above the glass transition temperature and below the melting point When heated, the nanocarbon polymer material 20 is fluidized in the thermoplastic polymer 20, and the nanocrystal polymer material 10 is immersed in the thermoplastic polymer 20 to produce the nanocarbon polymer composite 100 (FIG. 1B).

In one embodiment of the present invention, the thermoplastic polymer is heated at a temperature not higher than the glass transition temperature and lower than the melting point to a temperature lower than the glass transition temperature of the thermoplastic polymer, But the present invention is not limited thereto.

In one embodiment of the present invention, the thermoplastic polymer is selected from the group consisting of polystyrene (PS), polyethylene (PE), polymethylmethacrylate (PMMA), polybenzimidazole (celazole) Polypropylene (PP), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polysulfone (PSU), and combinations thereof. But may not be limited thereto. The thermoplastic polymer has a characteristic of changing its shape upon application of heat and the temperature at which the shape of the thermoplastic polymer varies varies depending on the type of polymer. However, thermoplastic polymers commonly have inherent glass transition temperature and melting point, Can be used to immerse the nanotube material on a thermoplastic polymer without the use of a solvent.

In one embodiment of the present invention, the fluidity of the thermoplastic polymer may be increased by heating the thermoplastic polymer, but the present invention is not limited thereto. The heating temperature of the thermoplastic polymer may vary depending on the kind of the thermoplastic polymer, but may be in a range of the glass transition temperature of the thermoplastic polymer and the melting point of the thermoplastic polymer. The thermoplastic polymer exhibits considerable viscosity, elasticity, and stress strain at temperatures above the glass transition temperature, where fluidity is enhanced as if liquid, because the attraction between the polymer molecules is weakened.

In one embodiment of the present invention, the immersion of the nanotube material on the heated thermoplastic polymer may be performed by a difference in density of the nanotube material and the thermoplastic polymer, but may not be limited thereto . In particular, since the density of the nanotube material is greater than the density of the thermoplastic polymer, the nanotube material can sink into the thermoplastic polymer having increased fluidity.

In one embodiment of the invention, the nanotube material is selected from the group consisting of carbon nanotubes (CNTs), metal nanotubes, polymer nanotubes, boron nitride nanotubes, Si nanotubes, Si wires, But are not limited to, those selected from the group consisting of combinations of < RTI ID = 0.0 >

In one embodiment of the present invention, cooling of the thermoplastic polymer in which the nano channel substance is immersed may be performed at a temperature lower than the glass transition temperature of the thermoplastic polymer, but may not be limited thereto. The cooling temperature of the thermoplastic polymer differs depending on the kind of thermoplastic polymer used.

According to a second aspect of the present invention, there is provided a nanochannel polymer composite comprising a thermoplastic polymer prepared according to the manufacturing method of the first aspect of the present invention, wherein the nanochannel material is immersed.

Although the detailed description of the parts overlapping with the first aspect of the present application is omitted, the description of the first aspect of the present invention can be applied equally to the second aspect.

A third aspect of the invention provides a membrane comprising a nanotube polymer composite according to the second aspect of the present invention.

Although a detailed description of the second embodiment of the present invention is omitted, detailed description of the second aspect of the present invention can be applied to the third aspect, even if the description is omitted.

In one embodiment of the present invention, the membrane may be formed of a hole in a channel of the nanotube polymer composite, but the present invention is not limited thereto.

In one embodiment of the present invention, the membrane may form a nanochannel within the polymer to prevent water from passing through other parts of the channel, but may not be limited thereto.

In one embodiment of the present invention, the membrane may be used as a reverse osmosis membrane and an osmosis membrane, but may not be limited thereto.

In one embodiment of the present invention, since a solvent is not used in order to impart fluidity to the thermoplastic polymer, it is possible to omit the step of dissolving in a solvent environment-friendly and omitting elements harmful to the body and the environment, The problem that bubbles are formed in the thermoplastic polymer can be prevented. As a result, the present invention is capable of forming a desired channel inside the thermoplastic polymer by an environmentally friendly processing method, and the thermoplastic polymer can be recycled, thereby reducing resource waste.

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

[ Example ]

(CNT) is used in each of polystyrene (PS), polyethylene (PE), and polysulfone (PSU), which are commonly used for producing a nanotube polymer composite, Nano channels were formed. The CNT is a nanometer channel itself as a minute molecule having a diameter of several nanometers to several tens of nanometers, which is formed in a long dangle shape with carbon atoms connected by hexagonal rings. However, in order to use the CNT as a membrane, a polymer to fill the space between the CNTs was required. In order to obtain a membrane using the CNT, an experiment was conducted to form a nano channel inside the polymer.

In the conventional method of manufacturing a nanocarbon polymer composite by dissolving a polymer in a solvent in a membrane manufacturing method, since the solvent once evaporated and the remaining polymer leaves a portion occupied by the solvent as an empty space, the polymer dissolved in the solvent is dissolved in a CNT forest CNT forest), we could confirm the holes formed between the CNT forests after evaporating the solvent. The empty space was considerably difficult to remove if it remained as much as the volume occupied by the solvent, or if it was formed inside the polymer as air particles that remained between the CNTs. However, when the CNT is immersed in a vertical direction on the polymer, the polymer can be filled up from the bottom of the CNT without the empty space, The air in the space is pushed up by the polymer that has come in contact with the air, so that it is possible to prevent the formation of unnecessary air particles and voids.

Example  One: Polystyrene ( 폴리렌렌 , PS ) And carbon nanotubes ( carbon  nanotube, CNT Lt; RTI ID = 0.0 > Polymer  Manufacture of Composites

Nanotube polymer composites were prepared by forming channels with carbon nanotubes (CNTs) in a thermoplastic polymer, polystyrene (Sigma Aldrich, 331651). In order to form a CNT forest channel inside the polystyrene, Al 15 nm and Fe 1 nm were deposited on the Si substrate as the CNT forest using an E-beam evaporator and then subjected to WA-CVD (water-assisted chemical vapor deposition) MWCNT (multi walled carbon nanotubes) synthesized by the method was used. The CNT forest was placed on the polystyrene substrate and heated to increase the fluidity of the polystyrene, thereby immersing the CNT forest in the polystyrene. Specifically, 2 g of polystyrene beads (beads) was heated at a glass transition temperature (Tg) of 123 ° C. or less to remove moisture in the polystyrene, and then heated to a melting point of 240 ° C. or less. As the heating temperature increased, the polystyrene beads aggregated with each other to form one bulk polystyrene base material as the fluidity increased. Most polymers are sold in the form of beads, flakes, or powders, which are heated at temperatures above the glass transition temperature (Tg) to effect recrystallization and the recrystallized polymer has been Beads, flakes, or powders were merged into a bulk form. The heated polymer temperature was allowed to cool to below the glass transition temperature (Tg) to obtain a polymer having a flat surface.

The CNT forest prepared according to the present example was placed on the formed polystyrene substrate, and then heated to a temperature not lower than the glass transition temperature (Tg) of the melting point. The polystyrene gradually lost its viscosity and its fluidity increased, and the CNT forest on the polystyrene was immersed in the polystyrene substrate due to the difference in density. After the CNT forest was immersed, the heating temperature was lowered to a glass transition temperature (Tg) or lower to cool the polystyrene, thereby preparing a nanotube polymer composite in which a CNT forest was immersed in the polymer substrate.

In the method according to the first embodiment, when the temperature is raised according to the above-described process, since the polymer surrounds the outer wall and the outer wall of the nanochannel and thus does not provide a space for generating air bubbles, solvent or moisture bubbles remain in the polymer .

In order to observe the nano-channel polymer structure according to Example 1, it was confirmed by using an electron microscope. The results are shown in Fig.

FIG. 2 shows a CNT-immersed polystyrene composite prepared according to Example 1. FIG. FIG. 2A is a photograph of the polystyrene composite in which the CNT is immersed, and FIG. 2B is a schematic diagram of the polystyrene composite in which the CNT is immersed. FIGS. 2c to 2f show electron microscope images of the top, mid, and bottom (BOT) portions of the CNT-immersed polystyrene complexes shown in the schematic diagrams. As shown in FIGS. 2c to 2f, only polystyrene was observed because CNT was immersed in the upper portion of the complex (FIG. 2c). In the middle portion, polystyrene-only portion and CNT-immersed portion coexisted. (Fig. 2D and Fig. 2E), and it was confirmed that the CNT was immersed in the lower portion (Fig. 2F).

Example  2: polyethylene ( polyethylene , PE ) And carbon nanotubes ( carbon  nanotube, CNT Lt; RTI ID = 0.0 > Polymer  Manufacture of Composites

A nanotube polymer composite was prepared using polyethylene (Sigma Aldrich, 427772) as a thermoplastic polymer and carbon nanotube (CNT) as a nanochannel. The CNT-immersed polyethylene composite and the CNT forest were prepared in the same manner as in Example 1. First, 2 g of polyethylene, which is in the form of a bead, is heated to form a base material. Then, the CNT forest is placed on the base material and the glass transition temperature (Tg) is 106 ° C or higher, the melting point is 120 ° C to 180 ° C To form a CNT channel inside the polyethylene by dipping the CNT forest.

In order to observe the nano-channel polymer structure according to the second embodiment, it was confirmed using an electron microscope. The results are shown in Fig.

FIG. 3 is an electron microscope image of a CNT-immersed polyethylene composite according to Example 2, FIG. 3 (a) is an electron microscope image showing a cross section of the CNT-immersed polystyrene composite, (TOP), middle (MID), and bottom (BOT) portions of the CNT-immersed polyethylene composite. As shown in FIG. 3B to FIG. 3D, a polyethylene-only portion and a CNT-immersed portion coexist on the upper portion of the composite, and the boundary was observed (FIG. 3B). In the middle portion, polyethylene (FIG. 3C). It can be seen that the CNTs were completely immersed in the lower part, so that the polyethylene did not sink any more, and the boundary was formed (FIG. 3D).

Example  3: Polysulfone ( polysulfone , PSU ) And carbon nanotubes ( carbon nanotube , ≪ / RTI > CNT) Polymer  Manufacture of Composites

A nanotube polymer composite was prepared using polysulfone (Sigma Aldrich, 182443) as thermoplastic polymer and carbon nanotube (CNT) as a nanochannel. The CNT-immersed polyethylene or polysulfone complex and the CNT forest were prepared in the same manner as in Example 1. First, 2 g of polysulfone in the form of a bead is heated to produce a base material. Then, the CNT forest is placed on the base material and a glass transition temperature (Tg) of 185 ° C. or higher and a melting point of 343 ° C. or lower To form a CNT channel inside the polysulfone.

In order to observe the nanostructure polymer structure according to Example 3, it was confirmed by using an electron microscope. The results are shown in Fig.

4 is an electron microscope image of the CNT-immersed polysulfone composite produced according to the third embodiment. FIG. 4A is an electron microscope image showing a cross section of the polysulfone composite immersed with CNTs, FIGS. 4B to 4D are cross-sectional views of a polysulfone composite immersed in the CNT- ), And the lower part (BOT). 4B to 4D, polysulfone having CNTs immersed in the upper portion of the image was observed (FIG. 4B). In the middle portion, the CNTs were completely immersed so that the CNT-immersed portion and the polysulfone- (Fig. 4C), and it was confirmed that only the polysulfone was present in the lower part (Fig. 4D).

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

10: Nanochannel material
20: thermoplastic polymer
100: Nano-channel polymer composite

Claims (9)

Heating the thermoplastic polymer at a temperature above the glass transition temperature of the thermoplastic polymer and below the melting point of the thermoplastic polymer;
Immersing the nanotube material on the heated thermoplastic polymer; And
And cooling the thermoplastic polymer in which the nano channel material is immersed,
The immersion of the nanotube material on the heated thermoplastic polymer is performed by a difference in density between the nanotube material and the thermoplastic polymer,
The fluidity of the thermoplastic polymer is increased by heating the thermoplastic polymer,
The immersion of the nanotube material on the heated thermoplastic polymer is performed by a difference in density between the nanotube material and the thermoplastic polymer so that the thermoplastic polymer is heated from the bottom of the nanotube material to fill the void space Which can be filled without,
Wherein the nanochannel polymer composite is prepared by a method comprising the steps of:
The method according to claim 1,
Wherein the thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polymethyl methacrylate, polybenzimidazole, polypropylene, polyvinyl chloride, polytetrafluoroethylene, polysulfone, and combinations thereof / RTI > polymer nanocomposite composite.
delete delete The method according to claim 1,
Wherein the nanotube material comprises a material selected from the group consisting of carbon nanotubes, metal nanotubes, polymer nanotubes, boron nitride nanotubes, Si nanotubes, Si wires, and combinations thereof. ≪ / RTI >
The method according to claim 1,
Wherein the cooling of the thermoplastic polymer in which the nano channel substance is immersed is performed at a temperature not higher than the glass transition temperature of the thermoplastic polymer.
delete delete delete

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