KR101306634B1 - Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method - Google Patents
Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method Download PDFInfo
- Publication number
- KR101306634B1 KR101306634B1 KR1020110053894A KR20110053894A KR101306634B1 KR 101306634 B1 KR101306634 B1 KR 101306634B1 KR 1020110053894 A KR1020110053894 A KR 1020110053894A KR 20110053894 A KR20110053894 A KR 20110053894A KR 101306634 B1 KR101306634 B1 KR 101306634B1
- Authority
- KR
- South Korea
- Prior art keywords
- ethylenedioxythiophene
- dextran
- poly
- composition
- pedot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/02—Dextran; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 폴리(3,4-에틸렌디옥시티오펜)(poly(3,4-ethylenedioxythiophene); PEDOT) 중합체를 포함하는 조성물 및 그 제조방법에 관한 것으로서, 소정의 산화제에 물(H2O)을 용매로 사용하고 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)과 덱스트란 설페이트(Dextran Sulfate)를 도입하여 생성되는 수분산성 전도성 고분자인 폴리(3,4-에틸렌디옥시티오펜):덱스트란(PEDOT:Dextran) 공중합체를 포함하는 조성물 및 그 제조방법에 관한 것이다.
보다 더 상세하게 본 발명에 의하면, 물(H2O) 용매 하에서 하기 화학식 1의 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)에 하기 화학식 4의 덱스트란 설페이트(Dextran Sulfate)를 폴리음이온으로 적용하고, 산화제로 산화중합시킨 후, 상기 산화 중합에 의한 반응 혼합물을 이혼교환수지로 처리해줌으로써 생성되는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란(PEDOT:Dextran) 공중합체를 포함하는 조성물을 제공한다.
(화학식 1)
(화학식 4)
In more detail, according to the present invention, 3,4-ethylenedioxythiophene (EDOT) of the following Chemical Formula 1 in water (H 2 O) solvent Dextran sulfate (Dextran Sulfate) Poly (3,4-ethylenedioxythiophene) -dextran (PEDOT) air produced by applying polyanion as a polyanion, oxidatively polymerizing with an oxidizing agent, and then treating the reaction mixture by oxidative polymerization with a dimerization resin. Provided is a composition comprising coalescing.
(Formula 1)
(Formula 4)
Description
본 발명은, 폴리(3,4-에틸렌디옥시티오펜)(poly(3,4-ethylenedioxythiophene); PEDOT) 중합체를 포함하는 조성물 및 그 제조방법에 관한 것으로서, 소정의 산화제에 물(H2O)을 용매로 사용하고 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)과 덱스트란 설페이트(Dextran Sulfate)를 도입하여 생성되는 수분산성 전도성 고분자인 폴리(3,4-에틸렌디옥시티오펜):덱스트란(PEDOT:Dextran) 공중합체 및 그 제조방법에 관한 것이다.
The present invention relates to a composition comprising a poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxythiophene); PEDOT) polymer, and a method for producing the same, wherein water (H 2 O) Poly (3,4-ethylenedioxythiophene), a water-dispersible conductive polymer produced by using 3,4-ethylenedioxythiophene (EDOT) and dextran sulfate as a solvent, and introducing 3,4-ethylenedioxythiophene (EDOT) and dextran sulfate. ): Dextran (PEDOT: Dextran) copolymer and a method for producing the same.
지금까지 폴리티오펜(poly-thiophene)은 그 자체의 특유한 전기적/광학적 특성으로 인해 광범위하게 연구되어 왔다. 상기 폴리티오펜(poly-thiophene)은 화학적 산화/환원시 또는 전기화학적 산화/환원시 전기전도성이 된다. To date, polythiophenes have been extensively studied due to their unique electrical and optical properties. The polythiophene becomes electroconductive during chemical oxidation / reduction or electrochemical oxidation / reduction.
또한, 근래에 들어 티오펜(thiophene)의 3, 4번 위치에 치환체를 도입하여 용해성, 열안정성 및 내용제성을 증진시킨 폴리(3,4-에틸렌디옥시티오펜)(poly(3,4-ethylenedioxythiophene); PEDOT)이 개발되어 i) 대전 방지제, ii) 콘덴서 전해질 대용, iii) PCB 기판 코팅, iv) 유기 EL 디바이스의 구멍 분사층 등으로 응용되고 있다. In addition, poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxythiophene), which has recently introduced substituents at positions 3 and 4 of thiophene, has improved solubility, thermal stability and solvent resistance. PEDOT) has been developed to be used as i) antistatic agent, ii) condenser electrolyte substitute, iii) PCB substrate coating, iv) hole spray layer of organic EL device.
폴리(3,4-에틸렌디옥시티오펜)이 포함되는 공중합체 중 가장 일반적으로 사용되고 있는 폴리(3,4-에틸렌디옥시티오펜):폴리(스티렌술폰산)(PEDOT:PSS) 합성법에 의하면, 폴리(3,4-에틸렌디옥시티오펜)은 폴리음이온의 존재하에서 수성 용액, 비수성 용액 또는 분산액으로 제조되어진다. Among the copolymers containing poly (3,4-ethylenedioxythiophene), poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS) synthesis method, which is most commonly used, 3,4-ethylenedioxythiophene) is prepared as an aqueous solution, non-aqueous solution or dispersion in the presence of polyanions.
상기 폴리음이온으로 폴리(스티렌술폰산)을 이용하는데, 폴리(스티렌술폰산)을 이용할 경우, 폴리(3,4-에틸렌디옥시티오펜):폴리(스티렌술폰산)의 수계 분산액을 제조할 수 있다. Although poly (styrenesulfonic acid) is used as the polyanion, when poly (styrenesulfonic acid) is used, an aqueous dispersion of poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) can be prepared.
다만, 이와 같은 PEDOT:PSS는 PEDOT보다 PSS의 무게비율이 높을 경우로 합성되었을 때만 분산이 잘되므로, 용액 내의 PEDOT 비율의 조절이 어려운 문제점이 있고, 그 자체로 표면저항이 높아 전기전도성이 낮은 단점이 있었다. However, since PEDOT: PSS is well dispersed only when it is synthesized when the weight ratio of PSS is higher than that of PEDOT, it is difficult to control the PEDOT ratio in the solution. There was this.
따라서, PEDOT이 포함되는 수분산성 전도성 고분자를 합성하는 경우에 있어서, i) PEDOT의 비율을 높이고 폴리음이온의 비율을 낮추어도 분산이 잘되며, ii) 이에 따라 소정의 기질에 코팅시 표면저항이 낮아 전기전도성이 우수하며, iii) 코팅표면과 기질 사이에 접착력이 증가하는 물질 및 그 제조방법이 요구되고 있다.
Therefore, in the case of synthesizing a water-dispersible conductive polymer containing PEDOT, i) even if the ratio of PEDOT is increased and the ratio of polyanions is reduced, the dispersion is good. There is a need for a material having excellent electrical conductivity, and iii) a material having an increased adhesion between the coating surface and the substrate and a method of manufacturing the same.
본 발명은 전술한 종래기술의 문제점을 해결하기 위해 안출된 것으로서, 폴리(3,4-에틸렌디옥시티오펜)(poly(3,4-ethylenedioxythiophene); PEDOT)에 대비하여 낮은 폴리음이온의 비율에도 수계로의 분산이 용이한 폴리(3,4-에틸렌디옥시티오펜):덱스트란 공중합체(PEDOT:Dextran)를 포함하는 조성물 및 그 제조방법을 제공하는데 그 목적이 있다. The present invention has been made to solve the above-described problems of the prior art, it is water-based even at a low poly anion ratio compared to poly (3,4-ethylenedioxythiophene) (PEDOT) It is an object of the present invention to provide a composition comprising a poly (3,4-ethylenedioxythiophene): dextran copolymer (PEDOT: Dextran) which is easy to disperse into a furnace and a method of preparing the same.
또한, 본 발명은 폴리음이온에 대비한 폴리(3,4-에틸렌디옥시티오펜)(poly(3,4-ethylenedioxythiophene); PEDOT)의 비율증가에 따른 전기전도성 및 접착력이 향상된 폴리(3,4-에틸렌디옥시티오펜):덱스트란 공중합체(PEDOT:Dextran)를 포함하는 조성물 및 그 제조방법을 제공하는데 또 다른 목적이 있다. In addition, the present invention is a poly (3,4- improved electrical conductivity and adhesion according to the increase in the ratio of poly (3,4-ethylenedioxythiophene; PEDOT) compared to poly anion Another object is to provide a composition comprising ethylenedioxythiophene): dextran copolymer (PEDOT: Dextran) and a method of preparing the same.
본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 본 발명의 기재로부터 당해 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.
The technical objects to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical subjects which are not mentioned can be clearly understood by those skilled in the art from the description of the present invention .
전술한 종래기술의 문제점을 해결하기 위한 본 발명의 일측면에 의하면, 물(H2O) 용매 하에서 하기 화학식 1의 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)에 하기 화학식 4의 덱스트란 설페이트(Dextran Sulfate)를 폴리음이온으로 적용하고, 산화제로 산화중합시킨 후, 상기 산화 중합에 의한 반응 혼합물을 이혼교환수지로 처리해줌으로써 생성되는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란(PEDOT:Dextran) 공중합체를 포함하는 조성물을 제공한다.
According to an aspect of the present invention for solving the above-mentioned problems of the prior art, in the water (H 2 O) solvent 3,4-ethylenedioxythiophene (EDOT) of the general formula (1) Poly (3,4-ethylenedioxythiophene) produced by applying dextran sulfate of 4 as polyanion, oxidatively polymerizing with an oxidizing agent, and then treating the reaction mixture by the oxidative polymerization with a di-exchange resin. Provided is a composition comprising a PEDOT (Dextran) copolymer.
본 발명에서 상기 산화제는, 산화철, 암모늄퍼설페이트((NH4)2S2O8), 포타슘퍼설페이트(K2S2O8), 소듐퍼설페이트(Na2S2O8), 포타슘퍼옥소다이설페이트(K2O8S2), 삼염화철(Ferric Chloride; FeCl3), 삼브롬화철(FeBr3), 이염화구리(CuCl2), 이브롬화구리(CuBr2), 시안화철칼륨(K3Fe(CN)6), 황산철(Fe2(SO4)3), 과염소산철 (Fe(ClO4)3), 질산철(Fe(NO3)3), 염화몰리브덴(MoCl5), 염화루테늄(RuCl3), 과산화수소(H2O2), 황산(H2SO4), 페릭 토실레이트(Fe(OTs)3) 및 이들의 조합으로 이루어진 군에서 선택된 1종인 것이 바람직하다. In the present invention, the oxidizing agent, iron oxide, ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), potassium per Oxodisulfate (K 2 O 8 S 2 ), Ferric Chloride (FeCl 3 ), Iron Tribromide (FeBr 3 ), Copper Dichloride (CuCl 2 ), Copper Dibromide (CuBr 2 ), Potassium Cyanide ( K 3 Fe (CN) 6 ), iron sulfate (Fe 2 (SO 4 ) 3 ), iron perchlorate (Fe (ClO 4 ) 3 ), iron nitrate (Fe (NO 3 ) 3 ), molybdenum chloride (MoCl 5 ), It is preferable that it is one selected from the group consisting of ruthenium chloride (RuCl 3 ), hydrogen peroxide (H 2 O 2 ), sulfuric acid (H 2 SO 4 ), ferric tosylate (Fe (OTs) 3 ), and combinations thereof.
본 발명에서 상기 이온교환수지는, IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG, Lewatit SM-94, Lewatit monoplus S100H, Lewatit M600, Lewatit mp64ws 및 이들의 조합으로 이루어진 군에서 선택된 1종인 것이 바람직하다.In the present invention, the ion exchange resin, IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG It is preferred that it is one selected from the group consisting of Lewatit SM-94, Lewatit monoplus S100H, Lewatit M600, Lewatit mp64ws, and a combination thereof.
본 발명에서 상기 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)과 덱스트란 설페이트(Dextran Sulfate)의 혼합 비율은 1:1 내지 1:2.5 인 것이 바람직하다. In the present invention, the mixing ratio of 3,4-ethylenedioxythiophene (EDOT) and dextran sulfate (Dextran Sulfate) is preferably 1: 1 to 1: 2.5.
본 발명에서 상기 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체의 중량은, 1중량% 내지 4중량%인 것이 바람직하다. In the present invention, the weight of the poly (3,4-ethylenedioxythiophene) -dextran copolymer is preferably 1% by weight to 4% by weight.
본 발명은 상기 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 코팅 조성물을 포함한다. The present invention includes a coating composition comprising the poly (3,4-ethylenedioxythiophene) -dextran copolymer.
전술한 종래기술의 문제점을 해결하기 위한 본 발명의 타측면에 의하면, (a) 물(H2O) 용매하에서 하기 화학식 1의 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)과 하기 화학식 4의 덱스트란 설페이트(Dextran Sulfate)를 교반하는 단계; (b) 상기 (a)단계에서 생성되는 용액에 산화제를 넣고 교반하는 단계; 및 (c) 상기 (b)단계에서 생성되는 용액에 이온교환수지를 넣고 교반하는 단계;를 포함하는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체공중합체를 포함하는 조성물의 제조방법을 제공한다. According to another aspect of the present invention for solving the problems of the prior art described above, (a) 3,4-ethylenedioxythiophene (EDOT) of the formula (1) in a water (H 2 O) solvent And stirring the dextran sulfate (Dextran Sulfate) of the formula (4); (b) adding an oxidizing agent to the solution produced in step (a) and stirring the solution; And (c) adding an ion exchange resin to the solution produced in step (b) and stirring the poly (3,4-ethylenedioxythiophene) -dextran copolymer copolymer. To provide.
(화학식 1)(Formula 1)
(화학식 4)(Formula 4)
본 발명은, 상기 (c)단계 후에, 상기 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체에 계면활성제를 첨가하는 단계를 더 포함하는 것이 바람직하다. 이로써 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 코팅 조성물이 생성될 수 있다.
The present invention preferably further comprises adding a surfactant to the poly (3,4-ethylenedioxythiophene) -dextran copolymer after step (c). This may result in a coating composition comprising a poly (3,4-ethylenedioxythiophene) -dextran copolymer.
본 발명에 의하면, PEDOT에 대비하여 낮은 폴리음이온(Dextran Sulfate)의 비율에도 수계로의 분산이 용이한 PEDOT:Dextran 공중합체를 포함하는 조성물 및 그 제조방법을 제공하는 효과가 있다. According to the present invention, there is an effect of providing a composition comprising a PEDOT: Dextran copolymer which is easy to disperse in an aqueous solution even at a low polyanion (Dextran Sulfate) ratio compared to PEDOT, and a method of preparing the same.
또한, 본 발명에 의하면, 폴리음이온의 무게%의 감소로 인한 PEDOT의 비율증가에In addition, according to the present invention, the percentage of PEDOT increases due to a decrease in the weight% of polyanions.
따라 표면저항이 낮아져 전기전도도가 증가하고, 기질과의 접착력이 우수한 PEDOT:Dextran 공중합체를 포함하는 조성물 및 그 제조방법을 제공하는 효과가 있다. Accordingly, the surface resistance is lowered, the electrical conductivity is increased, and there is an effect of providing a composition comprising the PEDOT: Dextran copolymer having excellent adhesion to a substrate and a method of manufacturing the same.
또한, 본 발명에 의하면, 대전방지제, 태양전지 및 LED등에 일반적으로 사용되는 PEDOT:PSS을 대체하여 보다 경제적이고 효율적으로 이용될 수 있는 PEDOT:Dextran 공중합체를 포함하는 조성물을 제공하는 효과가 있다.
In addition, according to the present invention, there is an effect of providing a composition comprising a PEDOT: Dextran copolymer which can be used more economically and efficiently in place of PEDOT: PSS commonly used in antistatic agents, solar cells and LEDs.
도 1은 본 발명의 일실시예에 따른 PEDOT:Dextran의 UV-Vis 스펙트럼도.
도 2는 본 발명의 일실시예에 따른 PEDOT:Dextran의 TGA 그래프도.
도 3은 본 발명의 일실시예에 따른 PEDOT:Dextran의 FT-IR 스펙트럼도.1 is a UV-Vis spectrum diagram of PEDOT: Dextran in accordance with one embodiment of the present invention.
2 is a TGA graph of PEDOT: Dextran in accordance with one embodiment of the present invention.
3 is an FT-IR spectrum diagram of PEDOT: Dextran according to an embodiment of the present invention.
이하, 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 명세서에 기재된 실시예와 그 구성은 본 발명의 가장 바람직한 일실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Hereinafter, preferred embodiments of the present invention will be described in detail. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configuration thereof are only the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention, and various equivalents may be substituted for them at the time of the present application. It should be understood that there may be variations.
본 발명은 기존의 PEDOT:PSS의 문제점을 해결하기 위해, EDOT 단량체에 Dextran sulfate를 폴리음이온으로 적용하여, Na2S2O8, Fe2(SO4)3 등의 산화제 및 H2O용매하에서 PEDOT:Dextran 중합체를 합성하고, 이온교환수지를 도입하여 잔여이온이 제거하여 생성된 최종생성물 및 그 제조방법에 관한 것이다. In order to solve the problems of the conventional PEDOT: PSS, the present invention applies Dextran sulfate as a polyanion to an EDOT monomer, under an oxidizing agent such as Na 2 S 2 O 8 , Fe 2 (SO 4 ) 3 , and a H 2 O solvent. The present invention relates to a final product produced by synthesizing a PEDOT: Dextran polymer, and introducing an ion exchange resin to remove residual ions.
기존의 폴리(3,4-에틸렌디옥시티오펜):폴리(스티렌술폰산)[PEDOT:PSS]합성법에 의하면, 폴리(3,4-에틸렌디옥시티오펜)은 폴리음이온인 폴리(스티렌술폰산)의 존재하에서 수성 용액, 비수성 용액 또는 분산액으로 제조되어진다. According to the existing poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) [PEDOT: PSS] synthesis method, poly (3,4-ethylenedioxythiophene) is the presence of poly (styrenesulfonic acid) which is a polyanion. Under aqueous solution, non-aqueous solution or dispersion.
PEDOT:PSS는 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT) 단량체 및 폴리(스티렌술폰산)을 이용하여 중합반응에 의해 제조되는데, 하기의 화학식 1은 3,4-에틸렌디옥시티오펜의 구조를 나타내며, 하기의 화학식 2는 폴리(스티렌술폰산)의 구조를 나타낸다.
PEDOT: PSS is prepared by polymerization using 3,4-ethylenedioxythiophene (EDOT) monomer and poly (styrenesulfonic acid). The structure of the offene is shown, and the following formula (2) represents the structure of poly (styrenesulfonic acid).
(화학식 1)(Formula 1)
이와 같이 형성되는 PEDOT:PSS의 구조는 하기의 화학식 3과 같다. The structure of PEDOT: PSS formed as described above is represented by Chemical Formula 3 below.
이와 같은 PEDOT:PSS는 PEDOT:PSS이 약 '1:2.5'의 무게비로 합성되었을 때만 분산이 용이하므로, 용액 내의 PEDOT 비율의 조절이 어려운 문제점이 있고, 그 자체로 표면 저항이 높아 전기전도성이 낮은 단점이 있었다. Such PEDOT: PSS is easy to disperse only when PEDOT: PSS is synthesized at a weight ratio of about '1: 2.5', which makes it difficult to control the ratio of PEDOT in the solution, and in itself has high surface resistance and low electrical conductivity. There was a downside.
따라서, 본 발명은 PEDOT이 포함되는 수분산성 전도성 고분자를 합성하는 경우에 있어서, i) PEDOT의 비율을 높이고 폴리음이온의 비율을 낮추어도 분산이 잘되며, ii) 이에 따라 소정의 기질에 코팅시 표면저항이 낮아 전기전도성이 우수하며, iii) 코팅표면과 기질 사이에 접착력이 증가하는 물질을 염두에 두고 착안되었다. Therefore, the present invention, in the case of synthesizing the water-dispersible conductive polymer containing PEDOT, i) it is well dispersed even if the ratio of PEDOT is increased and the ratio of polyanion is reduced, ii) the surface upon coating a predetermined substrate accordingly It has low electrical resistance and excellent electrical conductivity. Iii) It was conceived with materials that increase adhesion between coating surface and substrate.
본 발명에 의한 폴리(3,4-에틸렌디옥시티오펜)-덱스트란(PEDOT:Dextran) 공중합체를 포함하는 조성물은, 물(H2O) 용매 하에서 하기 화학식 1의 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)에 하기 화학식 4의 덱스트란 설페이트(Dextran Sulfate)를 폴리음이온으로 적용하고, 산화제로 산화중합시킨 후, 상기 산화 중합에 의한 반응 혼합물을 이혼교환수지로 처리해줌으로써 생성될 수 있다. The composition comprising a poly (3,4-ethylenedioxythiophene) -dextran (PEDOT: Dextran) copolymer according to the present invention is a 3,4-ethylenedioxyti of the following formula (1) in a water (H 2 O) solvent By applying dextran sulfate of formula (4) to poly (anion) of off-phene (3,4-ethylenedioxythiophene; EDOT), oxidizing polymerization with an oxidizing agent, and treating the reaction mixture by oxidative polymerization with a divorce exchange resin Can be generated.
(화학식 1)(Formula 1)
(화학식 4)(Formula 4)
여기서, 상기 산화제는, 산화철, 암모늄퍼설페이트((NH4)2S2O8), 포타슘퍼설페이트(K2S2O8), 소듐퍼설페이트(Na2S2O8), 포타슘퍼옥소다이설페이트(K2O8S2), 삼염화철(Ferric Chloride; FeCl3), 삼브롬화철(FeBr3), 이염화구리(CuCl2), 이브롬화구리(CuBr2), 시안화철칼륨(K3Fe(CN)6), 황산철(Fe2(SO4)3), 과염소산철 (Fe(ClO4)3), 질산철(Fe(NO3)3), 염화몰리브덴(MoCl5), 염화루테늄(RuCl3), 과산화수소(H2O2), 황산(H2SO4), 페릭 토실레이트(Fe(OTs)3) 및 이들의 조합으로 이루어진 군에서 선택된 1종일 수 있다. Here, the oxidizing agent is iron oxide, ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), potassium peroxo Disulfate (K 2 O 8 S 2 ), Ferric Chloride (FeCl 3 ), Iron Tribromide (FeBr 3 ), Copper Dichloride (CuCl 2 ), Copper Dibromide (CuBr 2 ), Potassium Cyanide (K 3 Fe (CN) 6 ), iron sulfate (Fe 2 (SO 4 ) 3 ), iron perchlorate (Fe (ClO 4 ) 3 ), iron nitrate (Fe (NO 3 ) 3 ), molybdenum chloride (MoCl 5 ), chloride Ruthenium (RuCl 3 ), hydrogen peroxide (H 2 O 2 ), sulfuric acid (H 2 SO 4 ), ferric tosylate (Fe (OTs) 3 ), and a combination thereof.
또한, 상기 이온교환수지는, IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG, Lewatit SM-94, Lewatit monoplus S100H, Lewatit M600, Lewatit mp64ws 및 이들의 조합으로 이루어진 군에서 선택된 1종일 수 있다. In addition, the ion exchange resin, IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG, Lewatit SM-94, Lewatit monoplus S100H, Lewatit M600, Lewatit mp64ws and combinations thereof.
다만, 상기 산화제 및 이온교환수지는 반드시 이에 한정되는 것이 아니라, 발명의 필요에 따라 공지된 산화제 또는 이온교환수지를 이용하는 것도 가능할 것이다. However, the oxidizing agent and the ion exchange resin is not necessarily limited to this, it is also possible to use a known oxidizing agent or ion exchange resin according to the needs of the invention.
상기 3,4-에틸렌디옥시티오펜(3,4-ethylenedioxythiophene; EDOT)과 덱스트란 설페이트(Dextran Sulfate)은 1:1 내지 1:2의 무게비율로 혼합될 수 있는데, 이와 같이 최종생성물 내에 PEDOT의 비율을 증가시켜도 분산이 잘되며, 이에 따른 표면 저항의 감소와 전기전도도의 증가로 이어지는 장점이 있다. The 3,4-ethylenedioxythiophene (EDOT) and dextran sulfate (Dextran Sulfate) may be mixed in a weight ratio of 1: 1 to 1: 2. Even if the ratio is increased, the dispersion is good, and thus there is an advantage that leads to a decrease in surface resistance and an increase in electrical conductivity.
본 발명에서 상기 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체의 중량은, 1중량% 내지 4중량%인 것이 바람직하다. In the present invention, the weight of the poly (3,4-ethylenedioxythiophene) -dextran copolymer is preferably 1% by weight to 4% by weight.
이하 본 발명을 실시예를 통해 보다 상세히 설명한다. 다만, 하기의 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 이들 실시예에 의해서 제한되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for exemplifying the present invention, and the present invention is not limited to these examples.
[실시예 1]Example 1
덱스트란Dextran 설페이트를Sulfate 적용한 1.5 무게% 1.5% weight applied PEDOTPEDOT :: DextranDextran 수용액의 제조 Preparation of aqueous solution
(1) EDOT 1g과 Dextran sulfate 1g을 둥근 플라스크에 도입하고 탈이온수 86.87g에 녹인 후 한시간동안 메카니컬 교반기를 이용하여 교반한다. (1) 1 g of EDOT and 1 g of Dextran sulfate are introduced into a round flask, dissolved in 86.87 g of deionized water, and stirred using a mechanical stirrer for one hour.
(2) Na2S2O8 10g을 탈이온수 190g에 녹인 후 양이온 교환수지(lewatit monoplus S100H) 250g을 넣고 한시간 교반한 후 필터링한다. (2) After dissolving 10 g of Na 2 S 2 O 8 in 190 g of deionized water, add 250 g of a cation exchange resin (lewatit monoplus S100H), stir for 1 hour, and filter.
(3) 상기 (1)에서 생성된 용액에 Fe2(SO4)3 0.02g을 넣은 후 상기 (2)에서 생성된 용액 44.46g을 넣고 24시간동안 교반한 뒤, 양이온 교환수지인 lewatit monoplus S100H 26.6g, 음이온 교환수지인 lewatit M600 26.6g, lewatit mp64ws 13.3g를 넣고 각각을 30분씩 교반한다.(3) After adding 0.02 g of Fe 2 (SO 4 ) 3 to the solution produced in (1), 44.46 g of the solution produced in (2) was stirred for 24 hours, and then lewatit monoplus S100H, a cation exchange resin, was added. 26.6g, 26.6g of lewatit M600, anion exchange resin, and 13.3g of lewatit mp64ws were added and stirred for 30 minutes each.
(4) 상기 (3)에서 생성된 최종 생성물에 비이온성 계면활성제인 triton X-100 1% 수용액 한방울을 첨가한 후 폴리프로필렌 필름위에 바코터 RDS20을 사용하여 코팅한다. (4) A drop of 1% aqueous solution of triton X-100, which is a nonionic surfactant, is added to the final product produced in (3), and then coated on a polypropylene film using a bar coater RDS20.
(5) 이와 같은 과정을 거쳐서, 코팅된 필름의 표면저항을 측정하였고(측정기; Surface Resisitance Meter ; SRM-200), 테이프를 이용하여 접착력을 확인하였다.
(5) Through this process, the surface resistance of the coated film was measured (measurement; Surface Resisitance Meter; SRM-200), and the adhesive strength was checked using a tape.
[[ 실시예Example 2] 2]
덱스트란Dextran 설페이트를Sulfate 적용한 2 무게% 2 weight% applied PEDOTPEDOT :: DextranDextran 수용액의 제조 Preparation of aqueous solution
(1) EDOT 1g과 Dextran sulfate 1g을 둥근 플라스크에 도입하고 탈이온수 53.54g에 녹인 후 한시간동안 메카니컬 교반기를 이용하여 교반한다. (1) 1 g of EDOT and 1 g of Dextran sulfate are introduced into a round flask, dissolved in 53.54 g of deionized water and stirred using a mechanical stirrer for one hour.
(2) Na2S2O8 10g을 탈이온수 190g에 녹인 후 양이온 교환수지(lewatit monoplus S100H) 250g을 넣고 한시간 교반한 후 필터링한다. (2) After dissolving 10 g of Na 2 S 2 O 8 in 190 g of deionized water, add 250 g of a cation exchange resin (lewatit monoplus S100H), stir for 1 hour, and filter.
(3) 상기 (1)에서 생성된 용액에 Fe2(SO4)3 0.02g을 넣은 후 상기 (2)에서 생성된 용액 44.46g을 넣고 24시간동안 교반한 뒤, 양이온 교환수지인 lewatit monoplus S100H 26.6g, 음이온 교환수지인 lewatit M600 26.6g, lewatit mp64ws 13.3g를 넣고 각각을 30분씩 교반한다.(3) After adding 0.02 g of Fe 2 (SO 4 ) 3 to the solution produced in (1), 44.46 g of the solution produced in (2) was stirred for 24 hours, and then lewatit monoplus S100H, a cation exchange resin, was added. 26.6g, 26.6g of lewatit M600, anion exchange resin, and 13.3g of lewatit mp64ws were added and stirred for 30 minutes each.
(4) 상기 (3)에서 생성된 최종 생성물에 비이온성 계면활성제인 triton X-100 1% 수용액 한방울을 첨가한 후 폴리프로필렌 필름위에 바코터 RDS20을 사용하여 코팅한다. (4) A drop of 1% aqueous solution of triton X-100, which is a nonionic surfactant, is added to the final product produced in (3), and then coated on a polypropylene film using a bar coater RDS20.
(5) 이와 같은 과정을 거쳐서, 코팅된 필름의 표면저항을 측정하였고(측정기; Surface Resisitance Meter ; SRM-200), 테이프를 이용하여 접착력을 확인하였다.
(5) Through this process, the surface resistance of the coated film was measured (measurement; Surface Resisitance Meter; SRM-200), and the adhesive strength was checked using a tape.
[실시예 3][Example 3]
덱스트란Dextran 설페이트를Sulfate 적용한 2.5무게% 2.5% of applied weight PEDOTPEDOT :: DextranDextran 수용액의 제조 Preparation of aqueous solution
(1) EDOT 1g과 Dextran sulfate 1g을 둥근 플라스크에 도입하고 탈이온수 33.54g에 녹인 후 한시간동안 메카니컬 교반기를 이용하여 교반한다. (1) 1 g of EDOT and 1 g of Dextran sulfate are introduced into a round flask, dissolved in 33.54 g of deionized water, and stirred using a mechanical stirrer for one hour.
(2) Na2S2O8 10g을 탈이온수 190g에 녹인 후 양이온 교환수지(lewatit monoplus S100H) 250g을 넣고 한시간 교반한 후 필터링한다. (2) After dissolving 10 g of Na 2 S 2 O 8 in 190 g of deionized water, add 250 g of a cation exchange resin (lewatit monoplus S100H), stir for 1 hour, and filter.
(3) 상기 (1)에서 생성된 용액에 Fe2(SO4)3 0.02g을 넣은 후 상기 (2)에서 생성된 용액 44.46g을 넣고 24시간동안 교반한 뒤, 양이온 교환수지인 lewatit monoplus S100H 26.6g, 음이온 교환수지인 lewatit M600 26.6g, lewatit mp64ws 13.3g를 넣고 각각을 30분씩 교반한다.(3) After adding 0.02 g of Fe 2 (SO 4 ) 3 to the solution produced in (1), 44.46 g of the solution produced in (2) was stirred for 24 hours, and then lewatit monoplus S100H, a cation exchange resin, was added. 26.6g, 26.6g of lewatit M600, anion exchange resin, and 13.3g of lewatit mp64ws were added and stirred for 30 minutes each.
(4) 상기 (3)에서 생성된 최종 생성물에 비이온성 계면활성제인 triton X-100 1% 수용액 한방울을 첨가한 후 폴리프로필렌 필름위에 바코터 RDS20을 사용하여 코팅한다. (4) A drop of 1% aqueous solution of triton X-100, which is a nonionic surfactant, is added to the final product produced in (3), and then coated on a polypropylene film using a bar coater RDS20.
(5) 이와 같은 과정을 거쳐서, 코팅된 필름의 표면저항을 측정하였고(측정기; Surface Resisitance Meter ; SRM-200), 테이프를 이용하여 접착력을 확인하였다.
(5) Through this process, the surface resistance of the coated film was measured (measurement; Surface Resisitance Meter; SRM-200), and the adhesive strength was checked using a tape.
[[ 비교예Comparative example 1] One]
PSSPSS 를 적용한 1.5무게% 1.5% by weight PEDOTPEDOT :: PSSPSS 수용액의 제조 Preparation of aqueous solution
(1) EDOT 0.5g과 PSS 1.25g을 둥근 플라스크에 도입하고 탈이온수 92.96g에 녹인 후 한시간동안 메카니컬 교반기를 이용하여 교반한다. (1) 0.5 g of EDOT and 1.25 g of PSS are introduced into a round flask, dissolved in 92.96 g of deionized water and stirred using a mechanical stirrer for one hour.
(2) Na2S2O8 5g을 탈이온수 95g에 녹인 후 양이온 교환수지(lewatit monoplus S100H) 125g을 넣고 한시간 교반한 후 필터링한다. (2) After dissolving 5 g of Na 2 S 2 O 8 in 95 g of deionized water, add 125 g of a cation exchange resin (lewatit monoplus S100H), stir for 1 hour, and filter.
(3) 상기 (1)에서 생성된 용액에 Fe2(SO4)3 0.01g을 넣은 후 상기 (2)에서 생성된 용액 23.4g을 넣고 24시간동안 교반한 뒤, 양이온 교환수지인 lewatit monoplus S100H 13.3g, 음이온 교환수지인 lewatit M600 13.3g, lewatit mp64ws 6.65g를 넣고 각각을 30분씩 교반한다.(3) After adding 0.01 g of Fe 2 (SO 4 ) 3 to the solution produced in (1), 23.4 g of the solution produced in (2) was stirred for 24 hours, and then lewatit monoplus S100H, a cation exchange resin. 13.3g, 13.3g of lewatit M600, anion exchange resin, and 6.65g of lewatit mp64ws are added and stirred for 30 minutes each.
(4) 상기 (3)에서 생성된 최종 생성물에 비이온성 계면활성제인 triton X-100 1% 수용액 한방울을 첨가한 후 폴리프로필렌 필름위에 바코터 RDS20을 사용하여 코팅한다. (4) A drop of 1% aqueous solution of triton X-100, which is a nonionic surfactant, is added to the final product produced in (3), and then coated on a polypropylene film using a bar coater RDS20.
(5) 이와 같은 과정을 거쳐서, 코팅된 필름의 표면저항을 측정하였고(측정기; Surface Resisitance Meter ; SRM-200), 테이프를 이용하여 접착력을 확인하였다.
(5) Through this process, the surface resistance of the coated film was measured (measurement; Surface Resisitance Meter; SRM-200), and the adhesive strength was checked using a tape.
상기 실시예 1 내지 실시예 3 및 비교예에서 제시한 코팅 필름의 표면저항과 접착력 시험 결과는 하기의 표 1과 같다.
The surface resistance and adhesion test results of the coating films presented in Examples 1 to 3 and Comparative Examples are shown in Table 1 below.
상기의 표 1을 참조하면, PEDOT:PSS에 비해 PEDOT:Dextran의 수용액 내 중량조절이 자유로우며, PEDOT:Dextran의 중량이 늘어도 표면저항은 오히려 낮아지는 것을 확인할 수 있다. 또한, PEDOT:PSS에 비해 PEDOT:Dextran은 수용액 내 중량에 관계없이 접착력이 우수함을 확인할 수 있었다. Referring to Table 1, compared to PEDOT: PSS, the weight control in the aqueous solution of PEDOT: Dextran is free, and even if the weight of PEDOT: Dextran increases, the surface resistance is rather lower. In addition, it was confirmed that PEDOT: Dextran is superior in adhesive strength regardless of the weight in the aqueous solution compared to PEDOT: PSS.
따라서, PEDOT:Dextran이 PEDOT:PSS에 비해 표면저항이 낮고, 전기전도도가 높으며, 중량비율의 조절이 자유로와 물질의 활용도가 높음을 확인할 수 있다. 이와 같은 효과를 보다 더 상세하게 설명하기 위해 도 1 내지 도 3을 참조하기로 한다.
Therefore, PEDOT: Dextran has a lower surface resistance, higher electrical conductivity, and free control of the weight ratio than PEDOT: PSS, and it can be confirmed that the utilization of materials is high. In order to describe this effect in more detail, reference is made to FIGS. 1 to 3.
도 1은 본 발명의 일실시예에 따른 PEDOT:Dextran의 UV-Vis 스펙트럼도이다.1 is a UV-Vis spectrum diagram of PEDOT: Dextran according to an embodiment of the present invention.
PEDOT:Dextran의 UV-Vis 스펙트럼은 본 발명에 의해 합성된 수용성 전도성고분자의 전자구조 및 고분자사슬의 배향에 관한 정보를 얻기 위하여 측정되었다. PEDOT: Dextran's UV-Vis spectrum By the present invention It was measured to obtain information on the electronic structure of the synthesized water-soluble conductive polymer and the orientation of the polymer chain.
도 1을 참조하면, i) 400nm 이하에서 전자전이 및 폴라론 피크의 경향을 확인할 수 있고, ii) 750nm에서 편재화된 폴라론 피크를 확인할 수 있으며, iii) 1000nm 이상에서의 흡광도가 상승하는 것으로 비편재화된 전하운반체의 높은 이동도와 관련된 꼬리끌림현상을 확인할 수 있다.
Referring to FIG. 1, i) the trend of electron transition and polaron peaks at 400 nm or less, ii) localized polaron peaks at 750 nm, and iii) absorbance at 1000 nm or more are increased. The trailing phenomena associated with the high mobility of the delocalized charge carriers can be identified.
도 2는 본 발명의 일실시예에 따른 PEDOT:Dextran의 TGA 그래프도이다.2 is a TGA graph of PEDOT: Dextran according to an embodiment of the present invention.
PEDOT:Dextran의 TGA 그래프는 본 발명에 의해 합성된 수용성 전도성고분자의 열적안정성을 확인하기 위하여 측정되었다. 도 2를 참조하면, 171.62℃ 부터 고분자의 손실이 일어나기 시작하여, 281.66℃ 에서 완전히 열분해되는 것을 확인할 수 있다.
The TGA graph of PEDOT: Dextran is based on the present invention. The thermal stability of the synthesized water-soluble conductive polymers was measured. 2, the loss of the polymer starts to occur from 171.62 ℃, it can be seen that completely decomposed at 281.66 ℃.
도 3은 본 발명의 일실시예에 따른 PEDOT:Dextran의 FT-IR 스펙트럼도이다.3 is an FT-IR spectrum diagram of PEDOT: Dextran according to an embodiment of the present invention.
도 3을 참조하면, 1,500 ~ 1,151cm-1 부근에서는 C= C 비대칭 신축진동에 의한 피크가 나타났고, 1,300cm-1 부근에서는 내부사슬 Cβ-Cβ 신축진동에 의한 피크가 나타났고, 1,080cm- 1 에서의 C-O-C 변형피크로부터 PEDOT:Dextran이 합성되었음을 확인하였다.
Referring to FIG. 3, a peak due to C = C asymmetric stretching and vibration appeared around 1,500 ~ 1,151cm -1 , and a peak due to internal chain C β -C β stretching and vibration was found around 1,300cm -1 , 1,080 cm - from the peak of the modified COC 1 PEDOT: Dextran was confirmed that the synthesis.
이상 본 발명의 구체적 실시형태와 관련하여 본 발명을 설명하였으나 이는 예시에 불과하며 본 발명은 이에 제한되지 않는다. 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 범위를 벗어나지 않고 설명된 실시형태를 변경 또는 변형할 수 있으며, 본 발명의 기술사상과 아래에 기재될 특허청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능하다.The present invention has been described above in connection with specific embodiments of the present invention, but this is only an example and the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. Various modifications and variations are possible.
Claims (10)
(b) 상기 (a)단계에서 생성되는 용액에산화제를 넣고 교반하는 단계; 및
(c) 상기 (b)단계에서 생성되는 용액에이온교환수지를 넣고 교반하는 단계;
를 구비하는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 조성물의 제조방법.
(화학식 1)
(화학식 4)
(a) stirring 3,4-ethylenedioxythiophene (EDOT) of Formula 1 and Dextran Sulfate of Formula 4 in a water (H 2 O) solvent;
(b) adding an oxidizing agent to the solution produced in step (a) and stirring the solution; And
(c) stirring the ion exchange resin into the solution produced in the step (b);
A method for producing a composition comprising a poly (3,4-ethylenedioxythiophene) -dextran copolymer having a copolymer.
(Formula 1)
(Formula 4)
(d) 상기 (c)단계에서 생성되는 용액에 계면활성제를 첨가하는 단계를 더 구비하는 것을 특징으로 하는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 조성물의 제조방법.
The method of claim 1, wherein after step (c),
(d) a method for producing a composition comprising a poly (3,4-ethylenedioxythiophene) -dextran copolymer, further comprising the step of adding a surfactant to the solution produced in step (c). .
산화철, 암모늄퍼설페이트((NH4)2S2O8), 포타슘퍼설페이트(K2S2O8), 소듐퍼설페이트(Na2S2O8) 포타슘퍼옥소다이설페이트(K2O8S2), 삼염화철(Ferric Chloride; FeCl3), 삼브롬화철(FeBr3), 이염화구리(CuCl2), 이브롬화구리(CuBr2), 시안화철칼륨(K3Fe(CN)6), 황산철(Fe2(SO4)3), 과염소산철 (Fe(ClO4)3), 질산철(Fe(NO3)3), 염화몰리브덴(MoCl5),염화루테늄(RuCl3), 과산화수소(H2O2), 황산(H2SO4), 페릭 토실레이트(Fe(OTs)3) 및 이들의조합으로 이루어진 군에서 선택된1종인 것을 특징으로 하는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 조성물의 제조방법.
The method of claim 1, wherein the oxidizing agent,
Iron oxide, ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ) potassium peroxodisulfate (K 2 O 8 S 2 ), Ferric Chloride (FeCl 3 ), Iron Tribromide (FeBr 3 ), Copper Dichloride (CuCl 2 ), Copper Dibromide (CuBr 2 ), Potassium Cyanide (K 3 Fe (CN) 6 ) , Iron sulfate (Fe 2 (SO 4 ) 3 ), iron perchlorate (Fe (ClO 4 ) 3 ), iron nitrate (Fe (NO 3 ) 3 ), molybdenum chloride (MoCl 5 ), ruthenium chloride (RuCl 3 ), hydrogen peroxide Poly (3,4-ethylenedioxythiophene), characterized in that one kind selected from the group consisting of (H 2 O 2 ), sulfuric acid (H 2 SO 4 ), ferric tosylate (Fe (OTs) 3 ), and combinations thereof. A method for producing a composition comprising a) -dextran copolymer.
IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG, Lewatit SM-94, Lewatit monoplus S100H, Lewatit M600, Lewatit mp64ws 및 이들의 조합으로 이루어진 군에서선택된 1종인 것을 특징으로 하는 폴리(3,4-에틸렌디옥시티오펜)-덱스트란 공중합체를 포함하는 조성물의 제조방법.
The method of claim 1, wherein the ion exchange resin,
IONAC NM-60, IONAC NM-73, Dowex MB-46, Dowex MR-3, Amberite IRN-150, Amberite MB-20, MB-400, NRW-37, IONAC NM60 SG, Lewatit SM-94, Lewatit monoplus S100H , Lewatit M600, Lewatit mp64ws and a method for producing a composition comprising a poly (3,4-ethylenedioxythiophene) -dextran copolymer, characterized in that one selected from the group consisting of.
The poly (3,4-ethylenedioxythiophene) according to claim 1, wherein the weight of the poly (3,4-ethylenedioxythiophene) -dextran copolymer is 1% by weight to 4% by weight. A process for producing a composition comprising a dextran copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110053894A KR101306634B1 (en) | 2011-06-03 | 2011-06-03 | Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110053894A KR101306634B1 (en) | 2011-06-03 | 2011-06-03 | Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20120134754A KR20120134754A (en) | 2012-12-12 |
| KR101306634B1 true KR101306634B1 (en) | 2013-09-11 |
Family
ID=47902906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110053894A Expired - Fee Related KR101306634B1 (en) | 2011-06-03 | 2011-06-03 | Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101306634B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102094136B1 (en) | 2018-05-09 | 2020-03-27 | 전남대학교산학협력단 | Manufacturing method of environmentally-friendly super capacitor |
| CN116289206B (en) * | 2023-02-10 | 2025-01-03 | 江南大学 | A polythiophene-based photothermal fabric based on dextran sulfate as a template and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038224A1 (en) * | 1997-02-28 | 1998-09-03 | University Of Wollongong | Hydrodynamic electroprocessing of soluble conducting polymers |
| KR20050044681A (en) * | 2001-12-04 | 2005-05-12 | 아그파-게바에르트 | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
-
2011
- 2011-06-03 KR KR1020110053894A patent/KR101306634B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038224A1 (en) * | 1997-02-28 | 1998-09-03 | University Of Wollongong | Hydrodynamic electroprocessing of soluble conducting polymers |
| KR20050044681A (en) * | 2001-12-04 | 2005-05-12 | 아그파-게바에르트 | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 논문:Graduate School of the University of Massachusetts Amherst * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120134754A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101561595B1 (en) | Method for the production of conductive polymers | |
| JP5191171B2 (en) | Dispersant and dopant for conductive polymer synthesis, conductive polymer synthesized using the same, conductive composition containing the conductive polymer, dispersion of the conductive polymer or conductive composition, and the above Application of conductive polymer or conductive composition | |
| CN103534318B (en) | Electric conductive polymer suspension and preparation method thereof, conductive polymer material and electrolysis condenser and preparation method thereof | |
| TWI450907B (en) | Method for the preparation of conductive polymer dispersion, conductive polymer material made therefrom and solid electrolytic capacitor using the material | |
| Jeon et al. | A facile and rapid synthesis of unsubstituted polythiophene with high electrical conductivity using binary organic solvents | |
| CN101982486A (en) | Process for producing aqueous dispersion of composite of poly(3,4-dialkoxythiophene) with polyanion | |
| CN105295008B (en) | Electroactive polymer solution or coating, composition and method for forming same, capacitor and method for making same, and antistatic article | |
| CN103709417B (en) | A kind of polythiophene-based derivatives aqueous dispersion and preparation method thereof | |
| JP5323302B2 (en) | Method for producing conductive polymer paint and method for producing conductive coating film | |
| JP5758990B2 (en) | Novel polyvinyl sulfonic acid, process for producing the same, and use thereof | |
| KR101306634B1 (en) | Composition containing PEDOT:Dextran Copolymer and Its Manufacturing Method | |
| US20130100585A1 (en) | Electroconductive polymer suspension and method for producing the same, electroconductive polymer material, and solid electrolytic capacitor and method for producing the same | |
| CN103608284B (en) | The conductive nanometer particle of multiple structure and manufacture method thereof | |
| JP6266241B2 (en) | Conductive polymer composition and method for producing the same | |
| JP4501030B2 (en) | Conductive fine particles and method for producing the same | |
| JP5432319B2 (en) | Electronic device, conductive polymer composition and method for producing the same | |
| JP2014037504A (en) | Conductive composition and conductive film | |
| JP6724526B2 (en) | Water-soluble conductive polymer, method for producing the same, aqueous solution of the conductive polymer, and use thereof | |
| TWI675893B (en) | Antistatic coating composition with various surface resistance according to the dilution | |
| JP4501031B2 (en) | Conductive fine particles and method for producing the same | |
| TWI534219B (en) | Composition and method for forming electroactive polymer solution or coating comprising conjugated heteroaromatic polymer, electroactive polymer solution, capacitor and antistatic object comprising the electroactive coating, and solid electrolytic capaci | |
| JP4014458B2 (en) | Conductive polyaniline composition and method for producing the same | |
| JP6417452B2 (en) | Conductive polymer and method for producing the same | |
| JP5289212B2 (en) | Oxidizing agent for producing conductive polymer, solid electrolytic capacitor using the same, and method for producing the same | |
| KR101523751B1 (en) | A conductive polymer composition comprising a fluorine compound having an organic solvent dispersibility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
St.27 status event code: A-0-1-A10-A12-nap-PA0109 |
|
| PA0201 | Request for examination |
St.27 status event code: A-1-2-D10-D11-exm-PA0201 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-3-3-R10-R18-oth-X000 |
|
| D13-X000 | Search requested |
St.27 status event code: A-1-2-D10-D13-srh-X000 |
|
| D14-X000 | Search report completed |
St.27 status event code: A-1-2-D10-D14-srh-X000 |
|
| PG1501 | Laying open of application |
St.27 status event code: A-1-1-Q10-Q12-nap-PG1501 |
|
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
St.27 status event code: A-1-2-D10-D21-exm-PE0902 |
|
| E13-X000 | Pre-grant limitation requested |
St.27 status event code: A-2-3-E10-E13-lim-X000 |
|
| P11-X000 | Amendment of application requested |
St.27 status event code: A-2-2-P10-P11-nap-X000 |
|
| P13-X000 | Application amended |
St.27 status event code: A-2-2-P10-P13-nap-X000 |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
St.27 status event code: A-1-2-D10-D22-exm-PE0701 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
St.27 status event code: A-2-4-F10-F11-exm-PR0701 |
|
| PR1002 | Payment of registration fee |
Fee payment year number: 1 St.27 status event code: A-2-2-U10-U11-oth-PR1002 |
|
| PG1601 | Publication of registration |
St.27 status event code: A-4-4-Q10-Q13-nap-PG1601 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |
|
| FPAY | Annual fee payment |
Payment date: 20160711 Year of fee payment: 4 |
|
| PR1001 | Payment of annual fee |
Fee payment year number: 4 St.27 status event code: A-4-4-U10-U11-oth-PR1001 |
|
| P22-X000 | Classification modified |
St.27 status event code: A-4-4-P10-P22-nap-X000 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |
|
| FPAY | Annual fee payment |
Payment date: 20170721 Year of fee payment: 5 |
|
| PR1001 | Payment of annual fee |
Fee payment year number: 5 St.27 status event code: A-4-4-U10-U11-oth-PR1001 |
|
| FPAY | Annual fee payment |
Payment date: 20180627 Year of fee payment: 6 |
|
| PR1001 | Payment of annual fee |
Fee payment year number: 6 St.27 status event code: A-4-4-U10-U11-oth-PR1001 |
|
| PC1903 | Unpaid annual fee |
Not in force date: 20190905 Payment event data comment text: Termination Category : DEFAULT_OF_REGISTRATION_FEE St.27 status event code: A-4-4-U10-U13-oth-PC1903 |
|
| PC1903 | Unpaid annual fee |
Ip right cessation event data comment text: Termination Category : DEFAULT_OF_REGISTRATION_FEE Not in force date: 20190905 St.27 status event code: N-4-6-H10-H13-oth-PC1903 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |