KR20140118387A - Catechol graft copolymer, complex including the same and method for preparing thereof - Google Patents

Abstract

The present invention relates to a complex with further improved conductivity and photocatalyst effects by conjugating carbon fiber-based graphene, nanotubes, conductive metal, or titanium dioxide (TiO_2) with a polymer compound having a catechol group, and forming a complex with a polymer resin using carbon oxide fibers. According to an embodiment, the present invention provides a catechol complex with high conductivity and excellent photocatalyst effects, thereby being used for various industry fields such as a display, an image sensor, etc.

Description

TECHNICAL FIELD The present invention relates to a catechol graft copolymer, a catechol graft copolymer, a catechol graft copolymer,

The present invention relates to a polymer composite having a catechol group conjugated with a carbon fiber-based graphene or nanotube, a conductive metal or titanium dioxide (TiO ₂ ), and a carbonaceous oxide fiber to form a complex with a polymer resin, And a composite having a photocatalytic effect and a method for producing the same.

Transparent conductive films are widely used in fields that require both the purposes of light transmission and conductivity, such as image sensors, liquid crystal TVs, and light emitting displays. Currently widely used materials are indium tin oxide (ITO), which is easy to form a thin film on a glass substrate and has light transmission characteristics and excellent conductivity. The most important feature of Indium Tin Oxide (ITO) thin film is its excellent light transmittance, which is applied to various devices.

Indium tin oxide (ITO), however, has a problem in that it has an insufficient material value, coarse thin film surface and flexibility. In the case of an organic device, a thin film of indium tin oxide (ITO) The efficiency of the device is easily deteriorated by the oxygen transfer and the indium from the organic semiconductor to the organic semiconductor.

The technology that has been studied so far is mainly to make the metal have a width of several microns (占 width) from several microns (占 width), and make the area of the entire metal to be less than 10% of the total area, thereby making the transparency 80% or more. Metals such as silver (Ag), gold (Au), copper (Cu), nickel (Ni) and platinum (Pt) Indium Tin Oxide (ITO), which is a transparent electrode of conventional displays, has a high manufacturing cost due to a vacuum deposition process, low flexibility, high temperature process and other cracks due to multiple bending, Is not suitable as a transparent display transparent electrode due to the difference in thermal expansion coefficient of the display.

Korean Patent Application No. 10-2012-0056874

The present invention relates to a method for forming a composite comprising carbon fiber, polymer, metal oxide or titanium dioxide (TiO ₂ ) using a catechol having a reducing power and an effective coating power on various surfaces, And a method for producing the same.

One aspect of the present invention can provide a catechol graft copolymer conjugated with a polymer having a catechol group and a polyvinyl polymer, and a method for producing the same.

In another aspect of the present invention, the polymer having the catechol group is selected from the group consisting of 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxybenzylamine hydrobromide, deoxyepinephrine hydrochloride, catechin, catechin hydrate, protocatech acidic hydrate, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxybenzaldehyde, 4'-dihydroxyacetophenone hydrochloride (3 ', 4'-Dihydroxy-2-methylaminoacetophenone hydrochloride), 2-bromo-2' Bromo-2 ', 4'-dihydroxyacetophenone ) dopamine _{(dopamine, C 8 H 11 NO} 2), cafe ripening acid (caffeic acid) and the chloro-transgenic Seed (chlorogenic acid) of at least one catechol graft copolymer selected from the group comprising and can provide a production method thereof.

In one aspect of the present invention, the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone and polyvinyl pyridine, and a method for producing the same. .

In one aspect of the present invention, the catechol graft copolymer is a compound represented by the following formula (1)

Formula 1

Wherein x + y is 50 to 500, x / x + y is 0 to 0.9, y / x + y is 0.1 to 1, and a process for producing the same.

In addition, one aspect of the present invention relates to a method for producing a catechol-containing polymer, wherein the polymer having a catechol group and the catechol graft copolymer conjugated with the polyvinyl polymer are selected from the group comprising a carbon fiber-based material, a metal oxide-based compound or titanium dioxide (TiO ₂ ) At least one conjugated catheter conjugated complex and a method of producing the same.

Further, one aspect of the present invention can provide a catechol conjugation complex in which the catechol graft copolymer is conjugated with a carbon fiber-based material, and a method for producing the same.

In addition, one aspect of the present invention can provide a catechol conjugation complex in which the catechol graft copolymer is conjugated with a carbon fiber-based material and a metal oxide-based compound, and a method for producing the same.

Further, one aspect of the present invention can provide a catechol conjugation complex in which the catechol graft copolymer is conjugated with a carbon fiber-based material, a metal oxide-based compound, and titanium dioxide (TiO ₂ ), and a method for producing the same.

In another aspect of the present invention, the polymer having the catechol group is selected from the group consisting of 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxybenzylamine hydrobromide, deoxyepinephrine hydrochloride, catechin, catechin hydrate, protocatech acidic hydrate, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxybenzaldehyde, 4'-dihydroxyacetophenone hydrochloride (3 ', 4'-Dihydroxy-2-methylaminoacetophenone hydrochloride), 2-bromo-2' Bromo-2 ', 4'-dihydroxyacetophenone ) dopamine _{(dopamine, C 8 H 11 NO} 2), cafe ripening acid (caffeic acid) and the chloro-transgenic Seed (chlorogenic acid) of at least one catechol conjugated complex selected from the group including, and can provide a production method thereof.

In an embodiment of the present invention, the polyvinyl polymer may be at least one selected from the group consisting of polyvinyl pyrrolidone or polyvinyl pyridine, Complexes and methods for their preparation.

In one aspect of the present invention, the catechol graft copolymer is a compound represented by the following formula (1)

Formula 1

      Wherein x + y is 50 to 500, x / x + y is 0 to 0.9, y / x + y is 0.1 to 1, and a process for preparing the same.

According to an aspect of the present invention, the carbon fiber-based material may be at least one material selected from the group consisting of graphene oxide, carbon nanotubes of a single layer, carbon nanotubes of a composite layer, And a method for producing the same can be provided.

In one aspect of the present invention, the metal oxide compound is a nanowire selected from the group consisting of gold (Au), silver (Ag), copper (Cu), iron (Fe) Catechol conjugation complexes and methods for their preparation can be provided.

According to one aspect of the present invention, a catechol complex having a higher conductivity and an excellent photocatalytic effect can be provided, thereby being usefully used in various industrial fields such as a display or an image sensor.

FIG. 1 is a cross-sectional view of a conductive composite coated on a polyethylene terephthalate (PET) surface by a rod coating method according to an embodiment of the present invention.
2 is a graph showing the results of 1H NMR structural analysis of a catechol conjugation complex prepared according to an embodiment of the present invention.
FIG. 3 is a graph showing catechol synthesis of the catechol graft copolymer prepared according to one embodiment of the present invention through UV-vis.
FIG. 4 is a graph showing whether a catechol graft copolymer prepared according to an embodiment of the present invention is synthesized with a metal oxide compound through a UV-vis.
FIG. 5 is a graph showing the catechol conjugation complex prepared according to an embodiment of the present invention by catechol synthesis through ATR-IR.
FIG. 6 is a photograph of a catechol conjugation copolymer and a metal oxide complex prepared according to an embodiment of the present invention, using SEM.
FIG. 7 is a photograph of a catechol conjugation copolymer and a carbon fiber / metal oxide composite prepared according to an embodiment of the present invention, using SEM.
FIG. 8 is a graph showing surface analysis of a catechol conjugation copolymer and carbon fiber / metal oxide composite prepared according to an embodiment of the present invention using EDX.
9 is a graph of a surface analysis of a catechol conjugation copolymer and a metal oxide complex according to an embodiment of the present invention, measured by XPS.
10 is a graph of a surface analysis of a catechol conjugation copolymer and a carbon fiber / metal oxide composite prepared according to an embodiment of the present invention through XPS.
FIG. 11 is a graph showing permeability of a catechol conjugation copolymer and carbon fiber / metal oxide composite prepared according to an embodiment of the present invention.
FIG. 12 is a front / rear photograph of a PET (polyethylene terephthalate) surface coated with a rod coating method using a catechol conjugation copolymer and a carbon fiber / metal oxide composite prepared according to an embodiment of the present invention.
13 is a graph showing conductivity of a catechol conjugation copolymer and a carbon fiber / metal oxide composite prepared according to an embodiment of the present invention.
14 is a graph showing a photocatalytic effect of a catechol conjugation copolymer prepared according to an embodiment of the present invention and a carbon fiber / metal oxide / titanium dioxide (TiO ₂ ) composite.
15 shows the synthesis of titanium dioxide (TiO ₂ ) through EDX to confirm the formation of a carbon fiber / metal oxide / titanium dioxide (TiO ₂ ) complex and a catechol conjugation copolymer prepared according to an embodiment of the present invention. Respectively.

The compound having a catechol functional group has properties that can be conjugated not only with surface adhesion but also with a carbon fiber-based graphene, a carbon nanotube, a conductive metal, or titanium dioxide (TiO ₂ ) through a reduction reaction.

Carbon fiber-based graphene and nanotubes are artificial nanomaterials that can transmit currents at 100 times higher than silicon per unit area and at least 100 times higher than copper at room temperature. In addition, the thermal conductivity is more than two times higher than that of diamond, the mechanical strength is more than 200 times stronger than steel, and the elasticity is good.

These excellent properties result from the electronic arrangement of the hexagonal carbon structure. However, since graphene does not dissolve in solvents, it has many limitations in application. In order to dissolve in the solvent, graphene must be oxidized to produce soluble graphene oxide, but the graphene oxide loses its inherent conductivity. Therefore, the graphene or nanotube is again given conductivity while undergoing a reduction process to restore the conductivity.

In addition, titanium dioxide (TiO ₂ ) is one of the photocatalysts, which is a mediator that allows the chemical reaction to be promptly accelerated or slowed when a typical light is received, and is known to be harmless to the human body and chemically and physically stable. Titanium dioxide (TiO ₂ ) has a disadvantage in that it needs to be irradiated with light, but it can be advantageous in terms of physical properties through mixing with other materials. Recently, silver (Ag) nanoparticles It is used to reduce the resistance value by producing a mixture.

Polymers with catechol groups are common and universal complexes that can be applied to any substrate type or form and are thus widely applied in many fields. In addition, the catechol functional group can be coated on any surface and is used as an excellent metal reducing active material.

The catechol graft copolymer according to one aspect of the present invention is conjugated with a polymer having a catechol group in the above-mentioned polyvinyl polymer.

The polyvinyl polymer includes an amine (NH-) group, and can directly react with a catechol group to form a catechol graft copolymer. The polyvinyl polymer having such characteristics may be polyvinyl pyrrolidone, polyvinyl pyridine.

Also, the polymer having the catechol group contains a bisphenol group at the end of the compound and forms a quinone form at pH 8.5. Due to this characteristic, the polymer having a catechol group has an adhesive force and a coating force and enables a reducing action.

Examples of the polymer having a catechol group include 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxyacetophenone, (3,4-Dihydroxybenzylamine hydrobromide), Deoxyepinephrine hydrochloride, Catechin, Catechin hydrate, Protocatechuic acid, 3,4 Dihydroxybenzaldehyde, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxy-2 4-dihydroxy-2-methylaminoacetophenone hydrochloride, 2-bromo-2 ', 4'-dihydroxyacetophenone hydrochloride, dihydroxyacetophenone dopamine (C ₈ H ₁₁ NO ₂ ), caffeic acid and chlorogenic acid. .

In addition, the catechol graft copolymer according to one aspect of the present invention is conjugated to a main chain of a polymer having a catechol group, which is a component having polyvinyl pyrrolidone as a main chain and exhibiting an adhesive force or a reducing power.

The catechol graft copolymer according to one aspect of the present invention may have a molecular weight of 10,000 g / mol or more, and the copolymer matrix resin length may be adjusted to have such a molecular weight.

In addition, the catechol graft copolymer according to one aspect of the present invention may be a compound conjugated with a polymer having a catechol group in polyvinyl pyrrolidone, and specifically may be a compound represented by the following formula (1) have.

[Chemical Formula 1]

X + y is from 50 to 500, x / x + y is from 0 to 0.9, and y / x + y is from 0.1 to 1.

The catechol graft copolymer represented by Formula 1 may have a molecular weight of 1,000 to 1,000,000 g / mol, and more specifically 1,000 to 100,000 g / mol.

According to an aspect of the present invention, there is also provided a process for preparing a catechol graft copolymer comprising reacting a polymer having a catechol group with the catechol copolymer matrix.

The catechol copolymer host may be prepared by using polyvinyl pyrrolidone as a raw material, and polar solvents such as ethanol may be used as the solvent. . The solvent is preferably used in an amount of 40 to 80 parts by weight based on 100 parts by weight of the raw material.

After the catechol copolymer matrix is prepared as described above, a step of reacting the polymer having the catechol group with the matrix is carried out.

After the catechol copolymer copolymer is reacted with the polymer having the catechol group as described above, the carbon fiber-based material is bound by a reduction reaction in order to impart conductivity to the catechol graft copolymer according to one aspect of the present invention.

The carbon fiber-based material has conductivity itself, and when it is bonded to a metal oxide-based material having conductivity, the carbon fiber-based material fills the gap between the metal oxide-based materials due to its size characteristics, Can play a role.

The carbon fiber material may be selected from the group consisting of graphene oxide, carbon nanotubes of a single layer, and carbon nanotubes of a composite layer.

To prepare the catechol graft copolymer of the present invention as a composite containing conductivity, the catechol graft copolymer of the present invention as described above is first dissolved in a solvent.

As the solvent, a polar solvent may be used. For example, water may be used. The reaction may be carried out by adding a carbon fiber-based material dissolved in the same solvent to the catechol graft copolymer dissolved in the polar solvent.

Next, the catechol graft copolymer / carbon fiber-based material is dissolved in a solvent, and then the metal oxide-based compound having conductivity is dissolved in the same solvent and reacted. When the carbon fiber-based material / polymer / metal oxide- .

Then, after the complex of the carbon fiber material / polymer / metal oxide compound is dissolved in a solvent and then titanium dioxide (TiO ₂ ) is dissolved in the same solvent and reacted, the carbon fiber material / polymer / metal oxide compound / a titanium dioxide (TiO ₂₎ complex is formed.

In order to measure the conductivity of the composite, PET (polyethylene terephthalate) was used as the surface, and the film was coated using a 4-point probe apparatus.

The carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite coating according to the present invention thus prepared will be described in detail with reference to FIG.

1 is a cross-sectional view of PET (polyethylene terephthalate) rod-coated carbon fiber based material / polymer / metal oxide based compound / titanium dioxide (TiO ₂ ) composite according to an aspect of the present invention. As shown in FIG. 1, it can be seen that one aspect of the present invention is formed of a carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite.

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are for purposes of illustration only and are not intended to limit the scope of protection of the present invention.

Example 1. Formation of catechol at the terminal of polyvinyl pyrrolidone

4 g of polyvinyl pyrrolidone and 2 g of 2-chloro-3 ', 4'-dihydroxyacetophenone were charged in a 250 mL round bottom flask, 80 mL of ethanol was added. Thereafter, the reaction was carried out at 80 DEG C over 48 hours, and then the reaction product was purified with 400 mL of ether to obtain 5 g of a catechol graft copolymer in the form of powder. The results of the 1H NMR structural analysis of the catechol-conjugated copolymer thus obtained are shown in FIG.

Example 2. Formation of a composite in which a carbon fiber-based material is bonded to a catechol graft copolymer

100 ml of a solution prepared by dissolving 1 g of each of the catechol graft copolymers obtained in Example 1 in 100 ml of a trizma buffer solution (pH 8.5) and 1 mg / ml of oxidized graphene in distilled water was added, For 24 hours, centrifuged at 4000 rpm for 3 minutes by a centrifuge, and then dried in a freeze dryer to obtain 0.4 g of a carbon fiber-based material / polymer complex.

Example 3. Formation of a composite in which a metal oxide-based compound is bonded to a composite of a catechol graft copolymer / carbon fiber-based material

A solution prepared by dissolving 1 g of each of the complexes of the catechol graft copolymer / carbon fiber material obtained in Example 2 in 100 ml of a buffer solution of pH 8.5 and a solution of polyvinylpyrrolidone dispersed in isopropyl alcohol The silver (Ag) nanowire bound to polyvinyl pyrrolidone was diluted in 100 ml of distilled water to a concentration of 1 mg / ml, and the mixture was reacted at 25 ° C. for 24 hours. The mixture was centrifuged at 4000 rpm for 3 minutes , And then dried in a freeze dryer to obtain 0.3 g of a carbon fiber-based material / polymer / metal oxide-based compound composite. The result of the structural analysis of the obtained carbon fiber-based material / polymer / metal oxide-based compound composite by UV-vis is shown in FIG.

Example 4. Formation of a composite in which a metal oxide-based compound mixture is bonded to a catechol graft copolymer

A solution prepared by dissolving 1 g of each of the catechol graft copolymers obtained in Example 1 in 100 ml of a trizma buffer solution (pH 8.5) and a solution of polyvinyl pyrrolidone dissolved in isopropyl alcohol The silver (Ag) nanowire was diluted with 100 mg of distilled water to a concentration of 1 mg / ml, and the mixture was reacted at 25 ° C. for 24 hours. The resultant was centrifuged at 4000 rpm for 3 minutes and dried in a freeze dryer 0.32 g of a polymer / metal oxide-based compound composite was obtained.

Example 5 [0050] A carbon fiber-based material / polymer / metal oxide-based compound composite was coated with titanium dioxide (TiO ₂ ) Combined < / RTI >

Titanium dioxide (TiO ₂ ) was diluted with 100 mg of distilled water to a concentration of 30 mg / ml in a solution of 1 g of the carbon fiber-based substance / polymer / metal oxide-based compound complex obtained in Example 3 in 100 ml of a trizma buffer solution having a pH of 8.5 One solution is added and reacted at 25 캜 for 24 hours. Thereafter, the mixture was centrifuged at 4000 rpm for 3 minutes using a centrifuge, followed by drying in a freeze dryer to obtain 0.30 g of a carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite.

Practical Example 6. Formation and Sampling of Each Complex According to Concentration

The composites are formed according to the concentration of the metal oxide-based compound material in the production methods of Examples 3 to 4 above. Samples 1, 2, and 3 were composites bound by the manufacturing method of Example 3, and Samples 4, 5, and 6 were the same as those of Example 4, except that the concentrations of the metal oxide compound materials were 0.5, 1, and 2 mg / ≪ / RTI >

Example 7. Bar coating

A solution prepared by dissolving the carbon fiber-based substance / polymer / metal oxide-based compound complex obtained in Example 3 at a concentration of 10 ml / ml in isopropyl alcohol was sprayed on the surface of PET (polyethylene terephthalate) using a syringe, Coating is done using coating equipment.

Experimental Example 1. Confirmation of structure of carbon fiber material / polymer / metal oxide compound composite

The synthesis structures of the composites of Examples 1 to 4 were confirmed by 1H-NMR, UV-vis, ATR-IR, SEM, EDX and XPS, and the results are shown in FIG. 2 to FIG. From FIG. 2 to FIG. 11, the molecular structure characteristics of polymer synthesis, carbon fiber material / polymer composite, carbon fiber material / polymer / metal oxide compound composite formation were confirmed. FIG. 12 shows the results of stick coating And FIG. 13 is a graph showing the conductivity of the composite according to Example 3. FIG.

Specifically, FIG. 2 shows the results of 1 H-NMR analysis. In order to confirm the catechol synthesis of the catechol conjugation complex, 1 H-NMR analysis showed that the aromatics of the catechol can be confirmed between 6.0 and 7.5 ppm.

Figures 3, 4 and 14 are UV-vis analytical results. Figure 3 shows the catechol synthesis at 280 nm and 350 nm as a result of UV-vis analysis to confirm the catechol synthesis of the catechol conjugation complex. 4, in order to confirm the synthesis of the carbon fiber-based material / polymer composite and the carbon fiber-based material / polymer / metal oxide-based compound composite, the UV-vis analysis was conducted to find that the silver used as the metal oxide compound material at 355 nm and 390 nm (Ag) nanowires or silver (Ag) nanoparticles. FIG. 14 is a graph showing the results of a comparison between titanium dioxide (TiO ₂ ) and titanium oxide (TiO ₂ ) after the formation of a carbon fiber material / polymer / metal oxide compound / titanium dioxide It was confirmed by photocatalytic effect according to light irradiation time at 650 nm that methylene blue decreased with time.

5 shows the result of ATR-IR analysis. Catechol appearing in a range of complex conjugated catechol confirming the functional groups of the surface in order to determine whether the synthesis results, also 2800cm ^-1 a alkyl chain with 3,000 ~ 3,500cm ^-1 in the sample in the range, as indicated at 5, An aromatic functional group could be identified.

6, 7, and 16 are SEM analysis results. FIG. 6 shows the form of the complex by measuring the polymer / metal oxide compound complex at a magnification of 2000, 10000 and 50000 times. FIG. 7 shows the shape of the composite material after the carbon fiber-based material / polymer / metal oxide-based compound composite was formed and then measured at a magnification of 2000, 10000 and 50000, The plate shape of the carbon fiber material was confirmed. FIG. 16 shows the particle morphology of titanium dioxide (TiO ₂ ) measured at a magnification of 30,000 times after forming a carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite.

Figures 8 and 15 show the EDX analysis results. FIG. 8 shows EDX analysis of a catechol conjugation complex after forming a composite of a carbon fiber-based material and a metal oxide-based compound material. As a result, a carbon (C) element was identified at 0.2 to 0.5 eV and a silver (Ag) element at 3 eV . FIG. 15 shows the results of EDX analysis after forming a carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite. As a result, titanium (Ti) elements were observed at 0.4 to 0.6 eV and 4.4 to 4.6 eV.

Figures 9 and 10 show the XPS analysis results. The XPS analysis of the carbon fiber-based material / polymer composite and the carbon fiber-based material / polymer / metal oxide-based compound composite showed an O1s peak at 528 eV and an N1s peak at 399 eV. In addition, the C1s peak was confirmed at 285 eV, and unlike FIG. 9, the Ag 3d peak appeared at 375 eV and 368 eV in FIG. 10, confirming that the silver (Ag) element was bonded.

Experimental Example 2:

The carbon fiber-based material / polymer / metal oxide-based compound composite formed by the manufacturing method in Example 3 was dispersed in isopropyl alcohol at a concentration of 10 mg / ml, (Polyethylene terephthalate) surface at a speed of 10 mm / sec.

Experimental Example 3. Surface Transmittance / Complex Conductivity Measurement

The carbon fiber-based material / polymer / metal oxide-based compound composite and the polymer / metal oxide-based compound composite formed by the manufacturing method of Example 3 were coated on the surface of PET (polyethylene terephthalate) through rod coating as described in Experimental Example 4 . Then, the surface transmittance at 550 nm was analyzed by UV-vis analysis, and the results of conductivity measurement of each sample of the carbon fiber-based material / polymer / metal oxide-based compound composite through a 4-point probe instrument were shown in Table 1 And the measurement of the polymer / metal oxide composite was carried out as shown in Table 2 below. As shown in Fig.

division Metal oxide compound material concentration (mg / ml) Transmittance Conductivity (resistance value Ohm / sq) Remarks Sample A 0.5 58 480 Sample B One 56 420 Sample C 2 55 320

division Metal oxide based concentration (mg / ml) Transmittance Conductivity (resistance value Ohm / sq) Remarks Sample A 0.5 74 Not measured Sample B One 69 Not measured Sample C 2 55 2850

Experimental Example 4 Titanium dioxide (TiO ₂ ) Photocatalytic effect measurement by synthesis

UV-vis analysis of the carbon fiber-based material / polymer / metal oxide-based compound / titanium dioxide (TiO ₂ ) composite formed by the manufacturing method of Example 5 showed that the absorbance at 280 and 650 nm of methylene blue And thus the photocatalytic effect can be confirmed. These results are shown in Fig.

Claims (25)

A catechol graft copolymer conjugated with a polymer having a catechol group and a polyvinyl polymer. The method according to claim 1,
The polymer having the catechol group may be 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxy (3,4-Dihydroxybenzylamine hydrobromide), Deoxyepinephrine hydrochloride, Catechin, Catechin hydrate, Protocatechuic acid, 3,4 Dihydroxybenzaldehyde, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxy-2 4-dihydroxy-2-methylaminoacetophenone hydrochloride, 2-bromo-2 ', 4'-dihydroxyacetophenone hydrochloride, dihydroxyacetophenone dopamine (C ₈ H ₁₁ NO ₂ ), caffeic acid and chlorogenic acid. Wherein the catechol graft copolymer is a catechol graft copolymer. The method according to claim 1,
Wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone or polyvinyl pyridine. The method according to claim 1,
The catechol graft copolymer is a compound represented by the following formula (1)
Formula 1

Wherein x + y is from 50 to 500, x / x + y is from 0 to 0.9, and y / x + y is from 0.1 to 1. 2. The catechol graft copolymer according to claim 1, A catechol graft copolymer conjugated with a polymer having a catechol group and a polyvinyl polymer, and a catheter layer containing at least one conjugated catheter selected from the group consisting of a carbon fiber-based material, a metal oxide-based compound or titanium dioxide (TiO ₂ ) Call conjugation complex. 6. The method of claim 5,
Wherein the catechol graft copolymer is conjugated with a carbon fiber-based material. 6. The method of claim 5,
Wherein the catechol graft copolymer is conjugated with a carbon fiber-based material and a metal oxide-based compound. 6. The method of claim 5,
Wherein the catechol graft copolymer is conjugated with a carbon fiber-based material, a metal oxide-based compound, and titanium dioxide (TiO ₂ ). 9. The method according to any one of claims 5 to 8,
The polymer having the catechol group may be 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxy (3,4-Dihydroxybenzylamine hydrobromide), Deoxyepinephrine hydrochloride, Catechin, Catechin hydrate, Protocatechuic acid, 3,4 Dihydroxybenzaldehyde, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxy-2 4-dihydroxy-2-methylaminoacetophenone hydrochloride, 2-bromo-2 ', 4'-dihydroxyacetophenone hydrochloride, dihydroxyacetophenone dopamine (C ₈ H ₁₁ NO ₂ ), caffeic acid and chlorogenic acid. Lt; RTI ID = 0.0 > catechol < / RTI > conjugation complex. 9. The method according to any one of claims 5 to 8,
The polyvinyl polymer may be at least one selected from the group consisting of polyvinyl pyrrolidone and polyvinyl pyridine. The catechol conjugation complex 9. The method according to any one of claims 5 to 8,
The catechol graft copolymer is a compound represented by the following formula (1)
Formula 1

Wherein x + y is 50 to 500, x / x + y is 0 to 0.9, and y / x + y is 0.1 to 1. The catechol conjugation complex according to claim 1, 9. The method according to any one of claims 5 to 8,
Wherein the carbon fiber-based material is at least one material selected from the group consisting of graphene oxide, carbon nanotubes composed of a single layer, and carbon nanotubes composed of a composite layer. The method according to any one of claims 5, 7, and 8,
Wherein the metal oxide-based compound is one nanowire or nanoparticle selected from the group consisting of gold (Au), silver (Ag), copper (Cu), iron (Fe), or platinum (Pt). Placing a polymer having a catechol group and a polyvinyl polymer in a solvent; And
And reacting the solvent at 70 to 90 DEG C for 45 to 50 hours. 15. The method of claim 14,
The polymer having the catechol group may be 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxy (3,4-Dihydroxybenzylamine hydrobromide), Deoxyepinephrine hydrochloride, Catechin, Catechin hydrate, Protocatechuic acid, 3,4 Dihydroxybenzaldehyde, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxy-2 4-dihydroxy-2-methylaminoacetophenone hydrochloride, 2-bromo-2 ', 4'-dihydroxyacetophenone hydrochloride, dihydroxyacetophenone dopamine (C ₈ H ₁₁ NO ₂ ), caffeic acid and chlorogenic acid. Lt; RTI ID = 0.0 > catechol < / RTI > graft copolymer. 15. The method of claim 14,
Wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone and polyvinyl pyridine. 15. The method of claim 14,
The catechol graft copolymer is a compound represented by the following formula (1)
Formula 1

Wherein x + y is from 50 to 500, x / x + y is from 0 to 0.9, and y / x + y is from 0.1 to 1. 2. The method for producing a catechol graft copolymer according to claim 1, Placing a polymer having a catechol group and a polyvinyl polymer in a solvent;
Reacting the solvent at 70 to 90 DEG C for 45 to 50 hours;
Dissolving the carbon fiber material in a solution in which the catechol graft copolymer is reacted by the reaction;
Reacting the solution at 15 to 25 DEG C for 20 to 30 hours;
Dissolving a metal oxide compound in a solution in which the catechol conjugation complex is reacted by the reaction;
Reacting the solution at 15 to 25 DEG C for 20 to 30 hours;
Dissolving titanium dioxide (TiO ₂ ) in a solution in which the catechol conjugation complex by the reaction is dissolved; And
Reacting the solution in which the catechol conjugation complex and titanium dioxide (TiO ₂ ) are dissolved at 15 to 25 ° C for 20 to 30 hours. 19. The method of claim 18,
Placing the polymer having the catechol group and the polyvinyl polymer in a solvent;
Reacting the solvent at 70 to 90 DEG C for 45 to 50 hours;
Dissolving the carbon fiber material in a solution in which the catechol graft copolymer is reacted by the reaction; And
Reacting the solution at 15 to 25 DEG C for 20 to 30 hours. 19. The method of claim 18,
Placing the polymer having the catechol group and the polyvinyl polymer in a solvent;
Reacting the solvent at 70 to 90 DEG C for 45 to 50 hours;
Dissolving the carbon fiber material in a solution in which the catechol graft copolymer is reacted by the reaction;
Reacting the solution at 15 to 25 DEG C for 20 to 30 hours;
Dissolving a metal oxide compound in a solution in which the catechol conjugation complex is reacted by the reaction; And
Reacting the solution at 15 to 25 DEG C for 20 to 30 hours. 21. The method according to any one of claims 18 to 20,
The polymer having the catechol group may be 2-chloro-3 ', 4'-dihydroxyacetophenone, pyrocatechol, 3,4-dihydroxy (3,4-Dihydroxybenzylamine hydrobromide), Deoxyepinephrine hydrochloride, Catechin, Catechin hydrate, Protocatechuic acid, 3,4 Dihydroxybenzaldehyde, 4-methylcatechol, 4-tert-butylcatechol, 3 ', 4'-dihydroxy-2 4-dihydroxy-2-methylaminoacetophenone hydrochloride, 2-bromo-2 ', 4'-dihydroxyacetophenone hydrochloride, dihydroxyacetophenone dopamine (C ₈ H ₁₁ NO ₂ ), caffeic acid and chlorogenic acid. Lt; RTI ID = 0.0 > catechol < / RTI > conjugation complex. 21. The method according to any one of claims 18 to 20,
Wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone or polyvinyl pyridine. 21. The method according to any one of claims 18 to 20,
The catechol graft copolymer is a compound represented by the following formula (1)
Formula 1

Wherein x + y is 50 to 500, x / x + y is 0 to 0.9, and y / x + y is 0.1 to 1. 21. The method according to any one of claims 18 to 20,
Wherein the carbon fiber-based material is at least one material selected from the group consisting of graphene oxide, carbon nanotubes of a single layer, and carbon nanotubes of a composite layer. 21. The method according to claim 18 or 20,
Wherein the metal oxide compound is a nanowire or a nanoparticle selected from the group consisting of gold (Au), silver (Ag), copper (Cu), iron (Fe) Way.

Images