KR100374719B1 - Method for Preparation of the Soluble Poly(3,4-ethylenedioxythiophene) Powder - Google Patents
Method for Preparation of the Soluble Poly(3,4-ethylenedioxythiophene) Powder Download PDFInfo
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Abstract
본 발명은 다양한 유기용매에 가용성인 고분자 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법에 관한 것으로, 본 발명의 방법에 따르면, 일반식 (Ⅱ)의 도판트의 존재하에 3,4-에틸렌다이옥시싸이오펜 단량체를 산화제를 사용하여 중합시킨 후 건조시킴으로써 하기 일반식 (Ⅲ)의 가용성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a polymer poly (3,4-ethylenedioxythiophene) powder soluble in various organic solvents. According to the method of the present invention, 3, in the presence of a dopant of general formula (II) A method for producing soluble poly (3,4-ethylenedioxythiophene) powder of the following general formula (III) by polymerizing 4-ethylenedioxythiophene monomer with an oxidizing agent and then drying.
본 발명에 따라 합성된 가용성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 공기중에서 열적안정성, 대기안정성이 우수하고, 화학적 합성이 용이하며, 여러 가지 용매에 대한 용해도, 전기전도도, 투과도 등에 장점을 가지고 있다.Soluble poly (3,4-ethylenedioxythiophene) powder synthesized according to the present invention has excellent thermal stability and air stability in air, easy chemical synthesis, solubility in various solvents, electrical conductivity, permeability, etc. It has advantages
Description
본 발명은 다양한 유기용매에 가용성인 전도성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법에 관한 것이다.The present invention relates to a process for preparing conductive poly (3,4-ethylenedioxythiophene) powders soluble in various organic solvents.
지금까지 알려진 전도성고분자는 도핑에 의해 절연체로부터 반도체 및 전도체로의 전기적성질의 조절이 가능한 반면 기존의 기능성고분자와 비교시 기계적성질이나 가공성 등의 물리적성질이 떨어지는 단점을 가지고 있다.The conductive polymers known up to now have the disadvantage that physical properties such as mechanical properties and processability are inferior in comparison with conventional functional polymers, while controlling the electrical properties from the insulator to the semiconductor and the conductor by doping.
대부분의 전도성 고분자는 가시광선 영역의 빛을 흡수하기 때문에 투명도가많이 저하되는 단점을 가지고 있다. 따라서 이들 전도성고분자는 높은 투명성이 요구되지 않는 분야로의 사용으로 그 용도가 제한된다. 그러나 최근 독일의 Bayer사에서는 3,4-에틸렌다이옥시싸이오펜(EDOT) 이란 새로운 구조의 단량체를 선보였다. 이는 싸이오펜의 기본구조에 에틸렌다이옥시그룹을 링의 형태로 갖는 구조를 가지는 단량체로서, 이 3,4-에틸렌다이옥시싸이오펜 단량체를 전기화학적 또는 화학적으로 중합시 폴리(3,4-에틸렌다이옥시싸이오펜)(PEDOT)이란 물질로 전환된다 [에틸렌다이옥시기의 전자공여효과로 인하여 기존의 싸이오펜보다 낮은 광학적 밴드갭(1.6∼1.7eV)을 갖고 있다]. 이 폴리(3,4-에틸렌다이옥시싸이오펜)은 기존의 전도성고분자보다 높은 투명도를 보유하고 있다. 초창기 Bayer사에서는 모노머인 3,4-에틸렌다이옥시싸이오펜과 산화제를 알콜용매내에서 반응시켜 폴리(3,4-에틸렌다이옥시싸이오펜)을 알콜용액상태로 제조하였다. 최근에는 도판트로 폴리스티렌설포네이트(PSS)를 사용하고, EDOT을 수용액내에서 중합하여 수용액형태의 PEDOT을 제조하여 전기전도도, 열적안정성과 코팅성, 분산성 등에 있어서의 향상을 보이고 있다. 또한 EDOT의 알콜용액에 실리케이트를 첨가하고 여러 용도로의 코팅후 열처리를 통하여 강도, 경도 면에서의 추가적인 장점을 갖는 PEDOT을 제조하고 있다.Most conductive polymers have a disadvantage in that transparency is greatly reduced because they absorb light in the visible region. Therefore, these conductive polymers are limited in their use in fields where high transparency is not required. Recently, however, Bayer of Germany introduced a new structure of monomer called 3,4-ethylenedioxythiophene (EDOT). It is a monomer having a structure having an ethylenedioxy group in the form of a ring in the basic structure of a thiophene, and poly (3,4-ethylenedione when the 3,4-ethylenedioxythiophene monomer is electrochemically or chemically polymerized Oxythiophene) (PEDOT) is converted to a material [the optical bandgap (1.6-1.7 eV) is lower than that of the conventional thiophene due to the electron donating effect of ethylenedioxy group]. This poly (3,4-ethylenedioxythiophene) has a higher transparency than conventional conductive polymers. In the early days of Bayer, poly (3,4-ethylenedioxythiophene) was prepared in an alcohol solution by reacting a monomer 3,4-ethylenedioxythiophene with an oxidizing agent in an alcohol solvent. Recently, polystyrene sulfonate (PSS) is used as a dopant, and EDOT is polymerized in an aqueous solution to prepare PEDOT in the form of an aqueous solution, which shows improvement in electrical conductivity, thermal stability, coating property, and dispersibility. In addition, silicate is added to the alcohol solution of EDOT, and PEDOT having an additional advantage in terms of strength and hardness through heat treatment after coating for various uses is manufactured.
따라서, 본 발명의 목적은 상기와 같은 종래 기술과 차별화 하여, 제품 제조시 용액 상태가 아닌, 다양한 유기 용매에 가용성인 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for preparing poly (3,4-ethylenedioxythiophene) powder which is soluble in various organic solvents, which is not in solution state when manufacturing a product, different from the prior art as described above. .
본 발명자는 전술한 바와 같은 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조와 관련된 광범위한 연구 결과, 도판트의 존재하에 산화제를 사용하여 3,4-에틸렌다이옥시싸이오펜 단량체를 화학적인 방법으로 중합시켜 상기 다양한 유기용매에 가용성인 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하게 되어 본 발명을 완성하게 되었다.The inventors have found extensive research relating to the preparation of poly (3,4-ethylenedioxythiophene) powders as described above, in the presence of dopants. Using an oxidizing agent, the 3,4-ethylenedioxythiophene monomer Polymerization by a chemical method to prepare a poly (3,4-ethylenedioxythiophene) powder soluble in the various organic solvents to complete the present invention.
도 1은 본 발명의 방법에 따라 제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 FT-IR 측정 결과를 도시한 그래프이다.1 is a graph showing the results of the FT-IR measurement of the poly (3,4-ethylenedioxythiophene) powder prepared according to the method of the present invention.
도 2는 본 발명에 따른 방법으로 제조된, 디(2-에틸헥실)설포숙시네이트 음이온이 도핑된, 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 유기용매NMP (N-methyl-2-pyrrolidinone) 에 용해시켜 얻은 용액을 slide glass위에 회전주조(spin cast)시켜 얻어진 얇은 필름의 UV/Vis.-NIR 스펙트럼을 도시한 것이다.FIG. 2 shows a poly (3,4-ethylenedioxythiophene) powder doped with di (2-ethylhexyl) sulfosuccinate anion, prepared by the process according to the present invention, using an organic solvent NMP ( N- methyl- Figure 2 shows the UV / Vis.-NIR spectra of thin films obtained by spin casting a solution obtained by dissolving in 2-pyrrolidinone.
본 발명은 유기용매에 가용성인 고분자 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법을 제공하는 것으로서, 본 발명의 일면에 따르면, 일반식 (I)의 3,4-에틸렌다이옥시싸이오펜 단량체를 하기 일반식 (Ⅱ)의 도판트와 함께 0 ℃에서 산화제를 사용하여 30분 내지 72시간 동안 서서히 저어주면서 중합시킨 후 진공건조시켜 유기용매에 가용성인 하기 일반식 Ⅲ의 고분자 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법이 제공된다:The present invention provides a method for preparing a polymer poly (3,4-ethylenedioxythiophene) powder soluble in an organic solvent. According to one aspect of the present invention, 3,4-ethylenedioxy of general formula (I) The thiophene monomer was polymerized with a dopant of the following general formula (II) with agitation at 0 ° C. for 30 minutes to 72 hours and then dried under vacuum to be soluble in an organic solvent. A process for the preparation of 3,4-ethylenedioxythiophene) powder is provided:
상기 일반식 (Ⅰ)의 화합물은 에틸렌다이옥신 1,2번 탄소와 싸이오펜의 3,4번 탄소가 fused된 3,4-에틸렌다이옥시싸이오펜이다.The compound of the general formula (I) is 3,4-ethylenedioxythiophene fused with ethylenedioxine 1,2 carbon and 3,4 carbon of thiophene.
상기 일반식 (Ⅱ)로 나타낸 화합물은 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]이다. 여기서 R, R'은 2-에틸헥실기 이고, X는 설폰산 또는 설폰산의 나트륨염이다.The compound represented by the general formula (II) is di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid]. Wherein R and R 'are 2-ethylhexyl groups and X is sulfonic acid or sodium salt of sulfonic acid.
상기와 같이 일반식 (Ⅰ)의 단량체인 3,4-에틸렌다이옥시싸이오펜과 산화제 과황산암모늄(TCI)은 구입하여 진공증류에 의해 정제시킨 후 사용하였고, 일반식 (Ⅱ)의 도판트인 디(2-에틸헥실)설포숙신산의 나트륨염(일본 TCI S.0-139 제품)은 구입하여 그대로 사용하였으며, 디(2-에틸헥실)설포숙신산은 디(2-에틸헥실)설포숙신산의 나트륨염을 화학적으로 처리하여 사용하였다.As described above, 3,4-ethylenedioxythiophene and the oxidizing agent ammonium persulfate (TCI), which are monomers of general formula (I), were purchased and purified by vacuum distillation, and used as a dopant of general formula (II). Sodium salt of (2-ethylhexyl) sulfosuccinic acid (manufactured by Japan TCI S.0-139) was purchased and used as it was, while di (2-ethylhexyl) sulfosuccinic acid was sodium salt of di (2-ethylhexyl) sulfosuccinic acid. Was chemically treated.
0 ℃에서 0.4 mol의 3,4-에틸렌다이옥시싸이오펜과 0.2 mol의 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]을 1ℓ비이커내의 900㎖ 증류수에 넣어 자석 젓개로 저어준다. 이와 별도로 0.2 mol 과황산암모늄을 500㎖ 비이커내의 100㎖ 증류수에 넣어 자석젓개로 저어준다. 0 ℃에서 0.2 mol 과황산암모늄 용액을 3,4-에틸렌다이옥시싸이오펜과 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]과의 혼합물에 서서히 자석젓개로 저어주며 첨가한다. 반응물을 48시간 동안 자석젓개로 서서히 저어주며 방치한다.900 ml distilled water in 1 l beaker of 0.4 mol of 3,4-ethylenedioxythiophene and 0.2 mol of di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid) at 0 ° C. Stir in a magnetic saucer. Separately, 0.2 mol ammonium persulfate is added to 100 ml distilled water in a 500 ml beaker and stirred with a magnetic spoon. A 0.2 mol ammonium persulfate solution was slowly magnetized at a mixture of 3,4-ethylenedioxythiophene and di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid) at 0 ° C. Stir with a saucepan and add. Stir the reaction slowly with a magnetic stir for 48 hours.
반응이 끝난 후, 반응용액을 부흐너(Buchner) 깔때기에서 증류수로 세척하며 여과하고, 여과후 얻어진 조각을 진공라인과 연결된 건조튜브(drying tube)에 넣어 24시간동안 다이내믹(dynamic) 진공(10-3torr)하에 건조하여 아래의 일반식 Ⅲ과 같은 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하였다.After the reaction was over, the reaction solution was Buchner (Buchner) washed in the funnel with distilled water and filtered, put After filtering the resulting fragment in a drying tube (drying tube) connected to the vacuum line 24 hours dynamics (dynamic) vacuum (10 for - Dried under 3 torr) to prepare a poly (3,4-ethylenedioxythiophene) powder as shown in Formula III below.
상기 일반식 (Ⅲ)은 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]의 음이온 (A-)이 도핑된 폴리(3,4-에틸렌다이옥시싸이오펜)이다.The general formula (III) is a poly (3,4-ethylenedioxythio doped with an anion (A − ) of di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid). Offen).
본 발명의 다른 일면에 따르면, 본 발명의 상기 방법에 있어서 상기 도판트가, 비극성의 알킬 사슬인 2-에틸헥실기와 극성 설포숙시네이트기를 동시에 가지는, 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산 나트륨염]인 것을 특징으로 하는 전도성 고분자 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 제조방법이 제공된다.According to another aspect of the present invention, in the method of the present invention, the dopant is di (2-ethylhexyl) sulfosuccinic acid having a 2-ethylhexyl group which is a nonpolar alkyl chain and a polar sulfosuccinate group at the same time. Or di (2-ethylhexyl) sulfosuccinate sodium salt]. A method for producing a conductive polymer poly (3,4-ethylenedioxythiophene) powder is provided.
보다 구체적으로, 종래의 폴리(3,4-에틸렌다이옥시싸이오펜)의 제조방법은 단량체 EDOT을 수용액내에서 중합하여 수용액형태로 제조하는 것이었다. 그러나 본 발명은 일반식 (Ⅱ)로 표시되는 도판트의 존재하에 다음의 일반식 (Ⅰ)의 단량체인3,4-에틸렌다이옥시싸이오펜을 산화제를 사용하여 화학적 방법으로 중합시킨 후 건조시켜 분말을 제조함으로써 다양한 유기용매에 가용성인 일반식 (Ⅲ)의 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 합성하는 방법을 제공한다.More specifically, a conventional method for preparing poly (3,4-ethylenedioxythiophene) was to prepare monomer EDOT in an aqueous solution to polymerize it. However, in the present invention, in the presence of a dopant represented by the general formula (II), the polymer of 3,4-ethylenedioxythiophene, which is a monomer of the following general formula (I), is polymerized by an oxidizing agent and then dried to obtain a powder. It provides a method for synthesizing a poly (3,4-ethylenedioxythiophene) powder of the general formula (III) soluble in various organic solvents.
본 발명에 따른 방법으로 제조된, 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 일반 유기용매에 대한 용해성이 우수하며, 가공성이 큰 장점을 가지고 있다. 전도성뿐 아니라 가공성에 장점을 가지는 본 발명의 가용성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 metallization, 정전기 방지, 전자기파 흡수체, 전자기파 차폐용 도료 및 코팅 재료, 축전지, 캐퍼시터(capacitor)용 고분자 전해질, IR absorber, 광전화학 전지, PCB(printed circuit board) 위로의 전도성코팅, 전기변색소자 (ECD), 부식방지, 저항 가열(resistive heating), 케이블 실드(cable shielding), 마이크로파 흡수재료(microwave absorbor), 온도, 충격, 화학센서, 발광다이오드소자(LED), LED내의 hole 주입전극 및 hole 수송층 응용, 투명전도성전극, 전계효과트랜지스터(FET), PDLC (polymer dispersed liquid crystal) display, optical fiber, optical transducer, nano fiber 등에 응용 가능성이 큰 물질이다.The poly (3,4-ethylenedioxythiophene) powder prepared by the method according to the present invention has excellent solubility in general organic solvents and has great processability. The soluble poly (3,4-ethylenedioxythiophene) powder of the present invention, which has the advantages of conductivity as well as processability, is a polymer for metallization, antistatic, electromagnetic wave absorber, electromagnetic wave shielding paint and coating material, storage battery, and capacitor. Electrolytes, IR absorbers, photochemical cells, conductive coatings on printed circuit boards, electrochromic devices (ECDs), corrosion protection, resistive heating, cable shielding, microwave absorbers ), Temperature, shock, chemical sensor, light emitting diode (LED), hole injection electrode and hole transport layer application in LED, transparent conductive electrode, field effect transistor (FET), polymer dispersed liquid crystal (PDLC) display, optical fiber, optical It is a material that is highly applicable to transducers and nanofibers.
폴리(3,4-에틸렌다이옥시싸이오펜)을 기존의 보고된 방법과 같이하여 용액의 형태로 제조시 산업적인 적용이 용이한 장점을 가지고 있지만, 보관상의 어려움, 다양한 형태로의 가공, 다양한 용도로의 적용이 어려운 문제점을 가지고 있다.Although poly (3,4-ethylenedioxythiophene) has the advantage of being easy to be applied industrially when preparing a solution in the form of a solution as in the conventionally reported method, it is difficult in storage, processing into various forms, and various uses. It is difficult to apply the furnace.
본 발명에서는 상기의 문제점을 해결하기 위하여, 비극성 알킬사슬의 2-에틸헥실기와 극성작용기인 설포숙시네이트(sulfosuccinate)기를 동시에 가지는, 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]을 도판트로 사용하여 단량체인 3,4-에틸렌다이옥시싸이오펜과 산화제인 과황산암모늄을 0℃에서 일정시간 반응시킨 후 여과 및 세척, 건조시켜 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 합성하였다. 이와 같이 제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 포름산, 1-메틸-2-피롤리돈(NMP), 디메틸술폭시드(DMSO),N,N'-디메틸포름아미드(DMF) 등과 같은 극성용매 및o-클로로페놀,m-크레졸, 테트라히드로푸란(THF), 아세트산, 트리플루오로아세트산 등과 같은 극성의 정도가 약한 여러 유기용매 그리고 예컨대 클로로포름, 디클로로메탄, 벤젠 등과 같은 비극성 용매에 높은 용해도를 나타내었다.In the present invention, in order to solve the above problems, di (2-ethylhexyl) sulfosuccinic acid having a 2-ethylhexyl group of a nonpolar alkyl chain and a sulfosuccinate group which is a polar functional group at the same time [or di (2- Sodium salt of ethylhexyl) sulfosuccinic acid] was used as a dopant to react the monomer 3,4-ethylenedioxythiophene and ammonium persulfate as an oxidizing agent at 0 ° C for a certain time, followed by filtration, washing, and drying. 4-ethylenedioxythiophene) powder was synthesized. Thus prepared poly (3,4-ethylenedioxythiophene) powder is formic acid, 1-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N'- dimethylformamide (DMF Polar solvents such as) and various organic solvents having a weak polarity such as o -chlorophenol, m -cresol, tetrahydrofuran (THF), acetic acid, trifluoroacetic acid and the like, and nonpolar solvents such as chloroform, dichloromethane, benzene, etc. Showed high solubility.
이하에서는 본 발명의 방법에 따라, 다양한 유기용매에 가용성인 전도성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 합성방법을 구체적으로 설명하기로 한다.Hereinafter, according to the method of the present invention, a method for synthesizing a conductive poly (3,4-ethylenedioxythiophene) powder soluble in various organic solvents will be described in detail.
실시예 1Example 1
본 발명품인 다양한 유기용매에 가용성인 전도성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 합성법은 다음과 같다.Synthesis method of conductive poly (3,4-ethylenedioxythiophene) powder soluble in various organic solvents of the present invention is as follows.
단량체인 3,4-에틸렌다이옥시싸이오펜은 진공증류에 의해 정제시킨 후 사용하였고, 산화제인 과황산암모늄과 도판트인 디(2-에틸헥실)설포숙신산 나트륨염은 일본 TCI제품을 그대로 사용하였으며, 디(2-에틸헥실)설포숙신산은 디(2-에틸헥실)설포숙신산 나트륨염을 화학적으로 처리하여 사용하였다.The monomer 3,4-ethylenedioxythiophene was purified by vacuum distillation, and ammonium persulfate as an oxidant and di (2-ethylhexyl) sulfosuccinate sodium salt as dopant were used as TCI made in Japan. Di (2-ethylhexyl) sulfosuccinic acid was used by chemically treating di (2-ethylhexyl) sulfosuccinate sodium salt.
0℃에서 0.4 mol의 3,4-에틸렌다이옥시싸이오펜과 0.2 mol의 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산 나트륨염]을 1ℓ비이커내의 900㎖ 증류수(혹은 알콜)에 넣어 자석 젓개로 저어준다. 이와 별도로 0.1 mol (또는 0.2mol ~ 2 mol)의 과황산암모늄(혹은 톨루엔황산철)을 500㎖ 비이커내의 100㎖ 증류수(혹은 알콜)에 넣어 자석 젓개로 저어준다. 0 ℃에서 0.1 mol(혹은 0.2에서 2 mol) 과황산암모늄용액을 3,4-에틸렌다이옥시싸이오펜과 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염] 혼합용액에 서서히 첨가한다. 반응물을 48시간 동안 자석 젓개로 서서히 저어주며 방치한다.0.4 ml of 3,4-ethylenedioxythiophene and 0.2 mol of di (2-ethylhexyl) sulfosuccinic acid (or di (2-ethylhexyl) sulfosuccinic acid sodium salt) at 0 ° C in 900 ml distilled water Or alcohol) and stir with a magnetic spoon. Separately, 0.1 mol (or 0.2 mol to 2 mol) of ammonium persulfate (or iron toluene sulfate) is added to 100 ml distilled water (or alcohol) in a 500 ml beaker and stirred with a magnetic stirrer. 0.1 mol (or 0.2 to 2 mol) ammonium persulfate solution at 0 ° C. was mixed with 3,4-ethylenedioxythiophene and di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid. ] Add slowly to the mixed solution. Stir the reaction slowly with a magnetic stir for 48 hours.
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기에서 증류수(혹은 알콜)로 세척하며 여과하고, 여과후 얻어진 조각을 진공라인과 연결된 건조튜(drying tube)에 넣어 24시간동안 다이내믹(dynamic) 진공(10-3torr)하에 건조하였다.After the reaction, the reaction solution is washed with distilled water (or alcohol) in a Buchner funnel, filtered, and the resulting pieces are placed in a drying tube connected to a vacuum line for 24 hours. Dry under vacuum (10 -3 torr).
본 발명에서 화학적으로 제조된, 유기용매에 가용성인, 폴리(3,4-에틸렌다이옥시싸이오펜) 분말의 구조를 확인하기 위하여 FT-IR 스펙트럼의 측정결과, 1735 cm-1에서의 C=O (도판트인 디2-에틸헥실설포숙신산 또는 디2-에틸헥실설포숙신산의 나트륨 염) 진동 밴드(vibration band), 1517, 1323 cm-1에서의 C-C, C=C (싸이오펜) 신축진동(stretching vibration), 1198, 1141, 1087, 1052 cm-1에서의 C-O-C (3,4-에틸렌다이옥시싸이오펜)의 신축진동, 978, 839, 689 cm-1에서의 C-S(싸이오펜)의 진동밴드를 나타내어 일반식 (Ⅱ)에 나타낸 음이온이 도핑된 폴리(3,4-에틸렌다이옥시싸이오펜)이 합성되었음을 확인하였다(도 1 참조).Measurement of the FT-IR spectrum to confirm the structure of the poly (3,4-ethylenedioxythiophene) powder chemically prepared in the present invention, soluble in an organic solvent, C = O at 1735 cm -1 . (Sodium salt of dopant di2-ethylhexylsulfosuccinic acid or di2-ethylhexylsulfosuccinic acid) Vibration band, 1517, CC at 1323 cm −1 , C = C (thiophene) stretching vibration vibration), stretching vibration of COC (3,4-ethylenedioxythiophene) at 1198, 1141, 1087, 1052 cm - 1 , and CS (thiophene) vibration band at 978, 839, 689 cm- 1 It was confirmed that poly (3,4-ethylenedioxythiophene) doped with anions represented by the general formula (II) was synthesized (see FIG. 1).
건조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 포름산, 1-메틸-2-피롤리돈(NMP), 디메틸술폭시드(DMSO),N,N'-디메틸포름아미드(DMF) 등과 같은 극성 용매및o-클로로페놀,m-크레졸, 테트라히드로푸란(THF), 아세트산, 트리플루오로아세트산 등과 같은 극성정도가 약한 여러 유기용매, 그리고 클로로포름, 디클로로메탄, 벤젠 등과 같은 비극성 용매에 우수한 용해성을 나타내었다.Dried poly (3,4-ethylenedioxythiophene) powders include formic acid, 1-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N' -dimethylformamide (DMF), and the like. Excellent solubility in the same polar solvents and various organic solvents with weak polarity such as o -chlorophenol, m -cresol, tetrahydrofuran (THF), acetic acid, trifluoroacetic acid, and nonpolar solvents such as chloroform, dichloromethane, benzene, etc. Indicated.
제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 상기 다양한 유기용매에 녹인 용액으로부터 용액주조 (solution casting) 공정에 의해 표면상태가 매끈한, 유연성있는 필름을 얻을 수 있었다. 유연성있는 필름의 측정된 전기전도도는 용액제조시 사용된 용매에 따라 10-3∼ 80 S/cm의 값을 나타내었다.From the solution in which the prepared poly (3,4-ethylenedioxythiophene) powder was dissolved in the various organic solvents, a flexible film having a smooth surface state was obtained by a solution casting process. The measured electrical conductivity of the flexible film showed a value of 10 −3 to 80 S / cm depending on the solvent used in preparing the solution.
실시예 2Example 2
실시예 1과 동일한 방법으로 0℃에서 중합을 실시하되, 0.1 mol의 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]과 0.1 mol의 방향족설폰산(benzenesulfonic acid, toluenesulfonic acid, sulfosalicylic acid, 2- naphthalene sulfonic acid, 2,6-naphthalenedisulfonic acid, naphthol-amino- disulfonic acid, anthraquinonesulfonic acid, anthraquinonedisulfonic acid, etc.)](또는 방향족술폰산의 염)이 혼합된 도판트 또는 0.1 mol의 디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산 나트륨염]과 0.1mol의 메틸설페이트, 에틸설페이트 등의 알킬설페이트 (또는 디알킬설페이트)작용기를 포함하는 시약류가 각각 혼합된 혼합도판트를 사용하여 가용성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하였다.The polymerization was carried out in the same manner as in Example 1, except that 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid) and 0.1 mol of aromatic sulfonic acid ( benzenesulfonic acid, toluenesulfonic acid, sulfosalicylic acid, 2-naphthalene sulfonic acid, 2,6-naphthalenedisulfonic acid, naphthol-amino-disulfonic acid, anthraquinonesulfonic acid, anthraquinonedisulfonic acid, etc.) (or salts of aromatic sulfonic acid) Or Reagents comprising 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid (or di (2-ethylhexyl) sulfosuccinate sodium salt) and 0.1 mol of methylsulfate, ethylsulfate, alkylsulfate (or dialkylsulfate) functional groups Soluble poly (3,4-ethylenedioxythiophene) powders were prepared using mixed dopants mixed with each other.
1ℓ 비이커내의 900㎖ 증류수에 단량체 3,4-에틸렌다이옥시싸이오펜 그리고디(2-에틸헥실)설포숙신산 [또는 디(2-에틸헥실)설포숙신산의 나트륨염]과 방향족설폰산(또는 알킬설페이트, 디알킬설페이트작용기)과의 혼합도판트를 함께 넣고 자석젓개로 저어준다. 이와 별도로 0.1 mol (또는 0.2 mol ~ 2 mol) 과황산암모늄을 500㎖ 비이커내의 100㎖ 증류수에 넣어 자석 젓개로 저어준다. 0 ℃에서 0.1 mol (또는 0.2 mol ~ 2 mol) 과황산암모늄이 들어있는 용액을 3,4-에틸렌다이옥시싸이오펜 그리고 디(2-에틸헥실)설포숙신산[또는 디(2-에틸헥실)설포숙신산의 나트륨염]과 방향족설폰산(또는 알킬, 디알킬설페이트작용기)과의 혼합도판트가 혼합되어있는 용액에 서서히 첨가한다. 반응물을 48시간 동안 자석 젓개로 서서히 저어주며 방치한다.Monomer 3,4-ethylenedioxythiophene and di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid) and aromatic sulfonic acid (or alkylsulfate) in 900 ml distilled water in a 1 l beaker. , A mixed dopant with a dialkyl sulfate functional group) Put them together and stir with a magnetic spoon. Separately 0.1 mol (Or 0.2 mol to 2 mol) Ammonium persulfate is added to 100 ml distilled water in a 500 ml beaker and stirred with a magnetic stirrer. 0.1 mol at 0 ° C (Or 0.2 mol to 2 mol) The solution containing ammonium persulfate was mixed with 3,4-ethylenedioxythiophene and di (2-ethylhexyl) sulfosuccinic acid (or sodium salt of di (2-ethylhexyl) sulfosuccinic acid) and aromatic sulfonic acid (or alkyl, Mixed dopant with dialkylsulfate functionality) is slowly added to the mixed solution. Stir the reaction slowly with a magnetic stir for 48 hours.
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기에서 증류수(혹은 알콜)로 세척하며 여과하고, 여과후 얻어진 조각을 진공 라인과 연결된 건조튜브(drying tube)에 넣어 24시간동안 다이내믹(dynamic) 진공(10-3torr)하에 건조하였다. 제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 상기 다양한 유기용매 (실시예 1)에 녹인 용액으로부터 용액주조 (solution casting) 공정에 의해 유연성있는 필름을 제조할 수 있었다. 제조된 유연성있는 필름의 측정된 전기전도도는 용액제조시 사용된 용매에 따라 10-2∼ 150 S/cm의 값을 나타내었다.After the reaction, the reaction solution is washed with distilled water (or alcohol) in a Buchner funnel and filtered, and the resulting piece is placed in a drying tube connected to a vacuum line for 24 hours. Dry under vacuum (10 -3 torr). A flexible film was prepared by a solution casting process from a solution of the prepared poly (3,4-ethylenedioxythiophene) powder in various organic solvents (Example 1). The measured electrical conductivity of the produced flexible film showed a value of 10 −2 to 150 S / cm depending on the solvent used in preparing the solution.
실시예 3Example 3
실시예 1 혹은 2와 동일한 방법으로 중합을 수행하되, 각각 0.1 mol(또는 0.2 mol ∼ 2 mol)의 톨루엔설포네이트철, 황산암모늄 철(ferrous ammoniumsulfate), 황산철(Iron sulfate), 과염소산철(Iron perchlorate), 과망간산칼륨(potassium permanganate), 2크롬산칼륨(potassium di chromate)등을 산화제로서 사용하여 가용성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하였다.The polymerization is carried out in the same manner as in Example 1 or 2, except that 0.1 mol (or 0.2 mol to 2 mol) of toluenesulfonate iron, Soluble poly (3,4-) using ferrous ammoniumsulfate, iron sulfate, iron perchlorate, potassium permanganate, potassium dichromte, etc. Ethylenedioxythiophene) powder was prepared.
제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 1-메틸-2-피롤리돈(NMP), 디메틸설폭사이드 (DMSO),N,N'-디메틸포름아미드 (DMF),o-클로로페놀,m-크레졸, 테트라히드로푸란 (THF), 클로로포름, 디클로로메탄 등의 용매에 녹여 매끈한 표면의 유연성있는 필름을 제조할 수 있었다.The prepared poly (3,4-ethylenedioxythiophene) powder was prepared using 1-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N' -dimethylformamide (DMF), o- It was dissolved in solvents such as chlorophenol, m -cresol, tetrahydrofuran (THF), chloroform and dichloromethane to produce a smooth surface flexible film.
이들 용액으로 부터 캐스팅된 free standing film의 측정된 전기전도도는 용액제조시 사용된 용매에 따라 10-2∼ 100 S/cm의 값을 나타내었다.The measured electrical conductivity of the free standing films cast from these solutions ranged from 10 -2 to 100 S / cm depending on the solvent used in the preparation of the solution.
본 발명은 다양한 유기용매에 용해성이 우수한 전도성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말을 제조하는 것으로서, 본 발명에 의해 제조된 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 보관성, 높은 가공성에 따른 작업성의 향상, 다양한 형태로의 응용, 다양한 용도로의 적용 등을 가능케 할 수 있어 관련 산업체에 많은 영향을 미치리라 생각된다. 본 발명품인 가용성, 전도성 폴리(3,4-에틸렌다이옥시싸이오펜) 분말은 metallization, 정전기 방지, 전자기파 흡수체, 전자기파 차폐용 도료 및 코팅 재료, 축전지, 캐퍼시터(capacitor)용 고분자 전해질, IR absorber, 광전화학 전지, PCB(printed circuit board) 위로의 전도성코팅, 전기변색소자(ECD), 부식방지, 저항 가열(resistive heating), 케이블 실드(cable shielding), 마이크로파 흡수재료(microwave absorbor), 온도, 충격, 화학센서, 발광다이오드소자(LED), LED내의 hole 주입전극 및 hole 수송층 응용, 투명전도성전극, 전계효과트랜지스터(FET), PDLC (polymer dispersed liquid crystal) display, optical fiber, optical transducer, nano fiber 등으로의 응용이 가능하다.The present invention is to prepare a conductive poly (3,4-ethylenedioxythiophene) powder excellent in solubility in various organic solvents, the poly (3,4-ethylenedioxythiophene) powder prepared by the present invention is stored It is possible to improve the workability according to the high workability, high workability, application to various forms, application to various uses, etc., which will have a great influence on related industries. Soluble, conductive poly (3,4-ethylenedioxythiophene) powder of the present invention is a metallization, antistatic, electromagnetic wave absorber, coating and coating material for electromagnetic wave shielding, polymer electrolyte for capacitor, capacitor, IR absorber, photoelectric Chemical cells, conductive coatings over printed circuit boards, electrochromic devices (ECDs), corrosion protection, resistive heating, cable shielding, microwave absorbers, temperature, shock, Application of chemical sensor, light emitting diode (LED), hole injection electrode and hole transport layer in LED, transparent conductive electrode, field effect transistor (FET), polymer dispersed liquid crystal (PDLC) display, optical fiber, optical transducer, nano fiber, etc. The application of is possible.
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| KR101000496B1 (en) | 2008-09-19 | 2010-12-14 | (주)폴리메리츠 | Method of manufacturing nanoparticles of poly3,4-ethylenedioxythiophene |
| KR101016260B1 (en) | 2009-02-25 | 2011-02-25 | (주)수양켐텍 | Film speaker used anion surfactants of aqueous dispersed poly3,4-ethylenedioxythiophene, solutions produced according to said method |
| KR101203596B1 (en) | 2012-03-28 | 2012-11-21 | 주식회사진영케미칼 | Manufacturing process of antistatic coating composition for PET sheet |
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| KR100933441B1 (en) * | 2008-09-09 | 2009-12-23 | (주)수양켐텍 | Process for producing water-based poly(3, 4-ethylenedioxythiophene) solutions using anionic surfactants and the solutions |
| WO2011003197A1 (en) * | 2009-07-10 | 2011-01-13 | University Of Manitoba | In situ polymerization of conducting poly(3,4-ethylenedioxythiophene) |
| KR20200142897A (en) * | 2019-06-14 | 2020-12-23 | 주식회사 엘지화학 | Sulfur-carbon composite, positive electrode for lithium secondary battery and lithium secondary battery comprising the same |
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