KR20010112574A - Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight - Google Patents
Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight Download PDFInfo
- Publication number
- KR20010112574A KR20010112574A KR1020000031719A KR20000031719A KR20010112574A KR 20010112574 A KR20010112574 A KR 20010112574A KR 1020000031719 A KR1020000031719 A KR 1020000031719A KR 20000031719 A KR20000031719 A KR 20000031719A KR 20010112574 A KR20010112574 A KR 20010112574A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- polypyrrole
- sodium salt
- molecular weight
- dopant
- Prior art date
Links
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
- 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
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
Abstract
Description
본 발명은 여러 유기용매에 가용성인, 다양한 분자량의 폴리피롤의 제조방법에 관한 것이다.The present invention relates to a process for preparing polypyrroles of various molecular weights, soluble in various organic solvents.
폴리피롤은 폴리아닐린과 더불어 공기중에서 열적 대기안정성이 우수하고 전기적, 화학적 합성이 용이하며 높은 전기전도도를 나타내어 많은 연구대상이 되고 있는 전도성고분자이다. 폴리피롤은 1968년 이탈리아의 과학자 Dall'Olio에 의해 전기화학적 방법에 의해 처음으로 합성되었으며, 화학적방법으로도 합성되어질 수 있다. 화학적, 전기화학적 방법에 의해 합성된 폴리피롤은 α, α'-탄소간 결합을 갖는 것으로 알려져 있다.Polypyrrole, together with polyaniline, is an electrically conductive polymer that has become a subject of many studies because it has excellent thermal atmospheric stability in air, easy electrical and chemical synthesis, and high electrical conductivity. Polypyrrole was first synthesized in 1968 by the Italian scientist Dall'Olio by electrochemical methods and can also be synthesized by chemical methods. Polypyrroles synthesized by chemical and electrochemical methods are known to have α, α'-carbon interbonds.
그러나 Zeller 등은 폴리피롤의 결합에 대한 XPS 연구를 통하여, 전기화학적 방법으로 필름을 제조시 전류밀도에 따라 그 구조가 변화될 수 있다고 보고하였다.However, Zeller et al. Reported that the XPS study on the binding of polypyrrole may change the structure according to the current density when the film is manufactured by the electrochemical method.
폴리피롤은 열적 대기안정성이 좋으며 높은 전기전도도를 가지고 있으나 사슬간 또는 사슬내의 강한 인력과 결합때문에 일반적인 유기용매에 잘 용해되지 않아 전기화학적으로 합성된 시료에 대한 연구가 주로 연구되어왔다. 이러한 가공성의 문제점을 해결하기 위하여 많은 연구진에 의해 가용성 폴리피롤의 화학적인 합성이 시도되어왔다.Polypyrrole has good thermal atmospheric stability and high electrical conductivity. However, research has been mainly conducted on electrochemically synthesized samples because they do not dissolve well in general organic solvents due to the strong attraction and coupling between or within chains. To solve this processability problem, many researchers have attempted chemical synthesis of soluble polypyrrole.
주로 사용된 방법으로는 단량체인 피롤에 치환체를 도입하여 사슬간의 인력을 약화시켜 폴리피롤에 용해성을 부여한 것으로, 이때 주로 긴 알킬기가 치환된 단량체가 사용되었다. 그러나 최근 단량체 피롤에 치환체를 도입하지 않고 다양한 유기용매에 녹는 가용성 폴리피롤이 화학적인 방법에 의해 합성되어지고 있다.The method mainly used was to introduce a substituent to pyrrole, a monomer, to weaken the attraction between the chains and to give solubility to polypyrrole. At this time, a monomer substituted with a long alkyl group was used. However, recently, soluble polypyrrole that is soluble in various organic solvents without introducing a substituent into monomer pyrrole has been synthesized by a chemical method.
그러나, 긴 알킬사슬 작용기를 가지는 도데실벤젠설폰산(dodecyl benzenesulfonic acid; DBSA)을 도판트로 사용하여 제조된 폴리피롤의 경우, 주사슬간 상호작용(interchain interaction)이 약화되어 극히 제한적인 유기용매 (m-크레졸, THF, DMF 등)에 녹는 것으로 보고되었다. 이 방법에 의해 제조된 폴리피롤역시 또한 비극성인 긴 알킬사슬의 도판트를 사용하였으므로, 한정적인 용매에 대하여 용해성을 보이고 있을 뿐 아니라 용해도가 떨어지는 단점을 나타내고 있다.However, in the case of polypyrrole prepared by using dodecyl benzenesulfonic acid (DBSA) having a long alkyl chain functional group as a dopant, the interchain interaction is weakened and the organic solvent ( m ) is extremely limited. -Cresol, THF, DMF, etc.). The polypyrrole prepared by this method also used a non-polar long alkyl chain dopant, which shows a solubility in a limited solvent as well as a poor solubility.
기존의 용해성을 갖는 도데실벤젠설폰산(dodecylbenzenesulfonic acid; DBSA)을 도판트로 사용하여 제조된 폴리피롤 [J. Y. Lee, D. Y. Kim and C. Y. Kim, Synthetic Metals, 74 (1995) 103]의 경우 분자량이 낮은 저분자량의 폴리피롤이 제조된 것으로 도 1의 분자량 측정결과로 부터 확인되었다.Low molecular weight low molecular weight for polypyrrole [JY Lee, DY Kim and CY Kim, Synthetic Metals, 74 ( 1995 ) 103] prepared by using dodecylbenzenesulfonic acid (DBSA) having a conventional solubility as a dopant Polypyrrole of was prepared was confirmed from the molecular weight measurement results of FIG.
폴리피롤의 경우, 도판트가 도핑되지 않은, 중성상태의 폴리피롤 분자량을 측정하여야 폴리피롤 자체의 사슬길이를 추정할 수 있다. 그러나 도판트가 도핑된 상태에서의 폴리피롤 분자량을 측정한 후 이로부터 중성상태의 폴리피롤 자체의 분자량을 다음의 가정을 통하여 계산할 수 있다.In the case of polypyrrole, the chain length of the polypyrrole itself can be estimated by measuring the molecular weight of the polypyrrole in the neutral state, which is not doped with the dopant. However, after measuring the polypyrrole molecular weight in the dopant doped state, the molecular weight of the polypyrrole itself in the neutral state can be calculated through the following assumptions.
일반적으로 전도성폴리피롤은 피롤 단량체 3∼4개당 도판트 하나가 도핑된 구조를 갖는것으로 알려져있다. 본 발명에서는 100% 도핑된 폴리피롤의 경우 피롤 단량체 3개당 도판트 하나가 도핑된 구조를 갖는것으로 가정하여 폴리피롤의 분자량을 계산하였다.In general, it is known that the conductive polypyrrole has a structure doped with one dopant per 3 to 4 pyrrole monomers. In the present invention, the molecular weight of polypyrrole was calculated on the assumption that 100% doped polypyrrole had a doped structure per 3 pyrrole monomers.
기존의 용해성을 갖는 도데실벤젠설폰산(dodecylbenzenesulfonic acid; DBSA)을 도판트로 사용하여 제조된 폴리피롤 [J. Y. Lee, D. Y. Kim and C. Y. Kim, Synthetic Metals, 74 (1995) 103.]의 경우에서의 분자량 측정결과 도 1에서와 같이 무게평균분자량(Mw)은 13,441로 나타났다.Determination of molecular weight in the case of polypyrrole [JY Lee, DY Kim and CY Kim, Synthetic Metals, 74 ( 1995 ) As shown in FIG. 1, the weight average molecular weight (Mw) was 13,441.
피롤 단량체 3개의 분자량을 195, counter ion인 도데실벤젠설폰에이트이온의 분자량을 325로 계산하면 하나의 도데실벤젠설폰에이트 이온이 3개의 피롤 단량체에 도핑된 구조단위의 분자량은 520 으로 계산되어진다. 이때, 도데실벤젠설폰에이트 이온이 도핑되지 않은, 중성상태의 폴리피롤 자체만의 분자량은 5,040 정도로 추측된다. (13,441 x 195/520 = 5,040) 이는 기존의 방법에 의해 합성된 폴리피롤의 사슬길이가 약 77개의 피롤링에 해당함을 나타내고 있다.When the molecular weight of 3 pyrrole monomers is 195 and the molecular weight of dodecylbenzenesulfonate ion, which is a counter ion, is 325, the molecular weight of a structural unit doped with one dodecylbenzenesulfonate ion in three pyrrole monomers is calculated as 520. . At this time, the molecular weight of polypyrrole itself in the neutral state, which is not doped with dodecylbenzenesulfonate ion, is estimated to be about 5,040. (13,441 x 195/520 = 5,040) This indicates that the chain length of the polypyrrole synthesized by the conventional method corresponds to about 77 pyrolling.
이 결과로 부터 기존의 도데실벤젠설폰에이트 이온이 도핑된 폴리피롤에서 나타나는 가용성은 저분자량에 기인되는 것으로 추측할 수 있다.From these results, it can be assumed that the solubility of polypyrrole doped with conventional dodecylbenzenesulfonate ions is due to low molecular weight.
따라서, 본 발명의 목적은 상기와 같은 종래 기술의 문제점을 해결하여, 다양한 유기 용매에 높은 가용성을 갖는, 다양한 분자량 [도핑되지않은, 중성상태에서의 무게평균분자량(Mw)이 5,000 이상 300,000 이하]의 폴리피롤 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to solve the problems of the prior art as described above, having a high solubility in various organic solvents, a variety of molecular weight [un weighted average molecular weight (Mw) in the undoped, neutral state 5,000 to 300,000 or less] It is to provide a polypyrrole production method.
본 발명자들은 전술한 바와 같은 여러 유기용매에 가용성인, 다양한 분자량의 폴리피롤 제조를 광범위하게 연구한 결과, 기능성도판트를 사용하고, 합성조건 (산화제 투여 몰수, 투여시간, 투여횟수, 합성온도 등)의 조절을 통한 피롤 단량체의 화학적중합을 통하여 상기 폴리피롤을 제조할 수 있음을 알게 되어 본 발명을 완성하게 되었다.The present inventors have extensively studied the production of polypyrrole of various molecular weights, which are soluble in various organic solvents as described above, and use a functional dopant, and the synthetic conditions (mole number of oxidizer administration, administration time, administration frequency, synthesis temperature, etc.) The present invention was completed by knowing that the polypyrrole may be prepared through chemical polymerization of pyrrole monomer through the control of.
도 1은 기존의 가용성 폴리피롤(도데실벤젠설폰산이 도핑된 폴리피롤) 제조방법에 의해 제조된 폴리피롤의 분자량(GPC) 측정을 도시한 그래프이고,1 is a graph showing the molecular weight (GPC) measurement of polypyrrole prepared by a conventional method for preparing soluble polypyrrole (polypyrrole doped with dodecylbenzenesulfonic acid),
도 2는 본 발명에 따른 방법으로 제조된 폴리피롤의 분자량(GPC) 측정을 도시한 그래프이다2 is a graph showing the molecular weight (GPC) measurement of polypyrrole prepared by the method according to the present invention.
도 3은 본 발명의 방법에 따라 제조된 폴리피롤 분말의 FT-IR 스펙트럼측정 결과를 도시한 그래프이다.3 is a graph showing the results of FT-IR spectroscopy of the polypyrrole powder prepared according to the method of the present invention.
도 4는 본 발명에 따른 방법으로 제조된 폴리피롤의 UV/Vis-NIR 스펙트럼을 도시한 그래프이다.4 is a graph showing the UV / Vis-NIR spectrum of polypyrrole prepared by the method according to the present invention.
본 발명을 하기의 실시예들을 참조하여 상세히 설명한다.The invention is described in detail with reference to the following examples.
본 발명은 여러 유기용매에 가용성인, 다양한 분자량의 폴리피롤 제조방법을 제공하는 것으로서, -30℃ 이상 60℃ 까지의 온도조건하에 도판트가 녹아있는 수용액에 일반식 I의 피롤 단량체를 첨가한 후, 산화제가 들어 있는 수용액을 피롤단량체와 도판트가 들어있는 용액에 5초에서 60분에 걸쳐 떨어뜨리고, 30분에서 90시간의 반응시간에 걸쳐 중합시킨 후 진공건조시켜 일반식 Ⅲ의 여러 유기용매에 가용성인, 다양한 분자량의 전도성 폴리피롤의 제조방법이 제공된다:The present invention provides a method for producing polypyrrole of various molecular weight, which is soluble in various organic solvents, and after adding a pyrrole monomer of the general formula (I) to an aqueous solution in which a dopant is dissolved under a temperature condition of -30 ° C to 60 ° C, The aqueous solution containing the oxidant was dropped in the solution containing the pyrrole monomer and the dopant for 5 seconds to 60 minutes, polymerized over the reaction time of 30 minutes to 90 hours, and then vacuum-dried to various organic solvents of the general formula III. Methods of making conductive polypyrroles of various molecular weights, which are soluble, are provided:
(Ⅰ)(Ⅰ)
상기 일반식 (Ⅰ)의 화합물은 4개의 탄소와 1개의 5-고리 복소환을 갖는 피롤 단량체이다.The compound of general formula (I) is a pyrrole monomer having four carbons and one 5-ring heterocycle.
(Ⅲ)(Ⅲ)
상기 일반식 (Ⅲ)으로 나타낸 화합물은 A-(음이온) 가 디(2-에틸헥실)설포숙신산의 음이온이 도핑된 폴리피롤이다.A compound represented by the general formula (Ⅲ) is A - is a polypyrrole (anion) are the anion of sulfosuccinate di (2-ethylhexyl) doping.
상기 도판트는 일반식 II의 화합물이다.The dopant is a compound of formula II.
(Ⅱ)(Ⅱ)
상기 일반식 (Ⅱ)으로 나타낸 화합물은, X는 설폰산 또는 설폰산의 나트륨염인, 디(2-에틸헥실)설포숙신산[di(2-ethylhexyl)sulfosuccinic acid] 또는 디(2-에틸헥실)설포숙신산의 나트륨염[di(2-ethylhexyl)sulfosuccinate sodium salt ]이다.Di (2-ethylhexyl) sulfosuccinic acid] or di (2-ethylhexyl), wherein X is a sulfonic acid or a sodium salt of sulfonic acid. Di (2-ethylhexyl) sulfosuccinate sodium salt] of sulfosuccinic acid.
본 발명의 다른 일면에 따르면, 본 발명의 상기 방법에 있어서 상기 도판트가, 비극성의 알킬 사슬을 가지는 2-에틸헥실기와 극성 설포숙시네이트기를 가지는, 디(2-에틸헥실)설포숙신산 또는 디(2-에틸헥실)설포숙신산의 나트륨염인 것을 특징으로 하는 가용성, 전도성 폴리피롤의 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 having a nonpolar alkyl chain and a polar sulfosuccinate group, or A method for producing soluble, conductive polypyrrole is characterized in that it is a sodium salt of di (2-ethylhexyl) sulfosuccinic acid.
본 발명의 다른 일면에 따르면, 본 발명의 상기 방법에 있어서 상기 산화제가 과황산암모늄 [(NH4)2S2O8, ammonium persulfate]인 것을 특징으로 하는 전도성 폴리피롤의 제조방법이 제공된다.According to another aspect of the present invention, there is provided a method for producing a conductive polypyrrole, wherein the oxidant is ammonium persulfate [(NH 4 ) 2 S 2 O 8 , ammonium persulfate] in the method of the present invention.
보다 구체적으로, 본 발명은 다음의 일반식 Ⅰ의 단량체인 피롤과 일반식 Ⅱ로 표시되는 도판트를 종래의 전기화학적 방법에 의하지 않고 화학적 방법으로 중합시킴으로써 다양한 분자량을 갖는 가용성, 전도성 폴리피롤 제조방법을 제공한다.More specifically, the present invention provides a method for preparing soluble, conductive polypyrrole having various molecular weights by polymerizing pyrrole, which is a monomer of the general formula (I), and a dopant represented by the general formula (II) by a chemical method instead of a conventional electrochemical method. to provide.
본 발명에 따른 방법으로 제조된 폴리피롤은 다양한 분자량에 걸쳐 여러 유기용매에 우수한 용해성을 갖는 장점을 가지고 있다. 전기전도성뿐만 아니라 가공성에 장점을 가지는 본 발명의 가용성 폴리피롤은 정전기 방지, 전자기파 흡수체, 전자기파 차폐용 도료 및 코팅 재료, 투명전도성전극, 발광다이오드내의 hole 주입전극 및 hole 수송층 응용, 축전지, 캐퍼시터(capacitor)용 고분자 전해질, 광전화학 전지 (photoelectrochemical cell), 전기변색소자 (electrochromic display), 부식방지, 저항 가열(resistive heating), 케이블 실드(cable shielding), 마이크로파 흡수체 (microwave absorbor), 온도, 충격, 화학적 센서, nano fiber 가공, optical transducer 등에 응용 가능성이 큰 물질이다.Polypyrrole prepared by the process according to the invention has the advantage of having excellent solubility in various organic solvents over various molecular weights. The soluble polypyrrole of the present invention, which has advantages in electrical conductivity as well as processability, is antistatic, electromagnetic wave absorber, coating and coating material for electromagnetic wave shielding, transparent conductive electrode, hole injection electrode in light emitting diode and hole transport layer application, storage battery, capacitor Polymer electrolyte, photoelectrochemical cell, electrochromic display, corrosion protection, resistive heating, cable shielding, microwave absorber, temperature, shock, chemical sensor This material is highly applicable to nanofiber processing, optical transducer, etc.
오랜동안 폴리피롤은 열적 대기안정성이 좋으며 높은 전기전도도를 갖는 것으로 알려져왔으나 사슬간 및 사슬내의 강한 인력과 결합 때문에 일반적인 유기용매에 잘 용해되지 않았다.Polypyrrole has been known to have good thermal atmospheric stability and high electrical conductivity for a long time. However, polypyrrole does not dissolve well in general organic solvents due to strong attraction between and in chains.
그러나, 최근 화학적인 방법에 의해 일부 유기용매에서 낮은 용해도를 나타내는 가용성 폴리피롤의 합성이 보고되고 있다. 이 보고에서는 폴리피롤의 합성시 긴 알킬사슬의 작용기인 도데실벤젠설폰산(dodecylbenzene sulfonic acid, DBSA)을 도판트로 사용하였으며, 이때 긴 알킬사슬인 도데실(dodecyl)기에 의해 폴리피롤 주사슬간의 상호작용 (interchain interaction)이 약화되어 일부 유기용매에 녹는다고 보고되었다 [J.Y.Lee, D.Y.Kim, Synthetic metals 74(1995)].Recently, however, the synthesis of soluble polypyrrole with low solubility in some organic solvents has been reported by chemical methods. In this report, dodecylbenzene sulfonic acid (DBSA), a functional group of the long alkyl chain, was used as a dopant in the synthesis of polypyrrole, and the interaction between the polypyrrole main chains by the dodecyl group of the long alkyl chain ( It has been reported that interchain interaction is weakened and dissolved in some organic solvents (JYLee, DYKim, Synthetic metals 74 (1995)).
그러나, 기존의 긴 비극성 알킬사슬을 가지는 DBSA에 의해 도핑된 가용성 폴리피롤은 비극성인 클로로포름, 극성 정도가 낮은m-크레졸, 극성 인 THF, DMF 등과 같이 사용가능한 유기용매가 극히 한정되어 있으며, 이들에 대한 용해도도 매우 낮아 가공성이 떨어지는 단점을 가지고 있다. 또한 도데실벤젠설폰산으로 도핑된 폴리피롤의 경우 무게평균분자량(Mw)이 13,441 [도 1]로서 저분자량임을 알 수 있었다.However, soluble polypyrroles doped by DBSAs with existing long nonpolar alkyl chains have extremely limited organic solvents available such as nonpolar chloroform, low polar m -cresol, polar THF, DMF, and the like. Solubility is also very low has the disadvantage of poor workability. In addition, in the case of polypyrrole doped with dodecylbenzenesulfonic acid, the weight average molecular weight (Mw) was found to be low molecular weight as 13,441 [Fig. 1].
본 발명에서는 상기의 저분자량에 기인한 가용성 폴리피롤의 문제점들을 극복하고자 비극성인 알킬 사슬을 갖는 2-에틸헥실(2-ethylhexyl)기와 극성인 설포숙시네이트(sulfosuccinate)기를 동시에 가지는 디(2-에틸헥실)설포숙신산[di(2-ethyl hexyl)sulfosuccinic acid] 또는 디(2-에틸헥실)설포숙신산의 나트륨염 [di(2-ethylhexyl)sulfosuccinate sodium salt]을 도판트로 사용하고, 단량체인 피롤(pyrrole)과 산화제인 과황산암모늄 [(NH4)2S2O8, ammonium persulfate]을 일정시간 반응시켜 다양한 분자량을 가질 뿐 아니라 여러 유기용매 에컨대 포름산, 1-메틸-2-피롤리디논(NMP), 디메틸술폭시드(DMSO),N,N'-디메틸포름아미드(DMF),o-클로로페놀,m-크레졸, 테트라히드로푸란(THF), 아세트산, 트리플루오로아세트산, 클로로포름, 디클로로메탄, 벤젠 등에 용해성이 우수한 가용성 폴리피롤을 합성하였다.In the present invention, in order to overcome the problems of soluble polypyrrole due to the low molecular weight, di (2-ethyl having a 2-ethylhexyl group having a nonpolar alkyl chain and a sulfosuccinate group having a polarity at the same time Hexyl) sulfosuccinic acid [di (2-ethylhexyl) sulfosuccinic acid] or di (2-ethylhexyl) sulfosuccinate sodium salt] is used as a dopant, and the monomer pyrrole ) And the oxidizing agent ammonium persulfate [(NH 4 ) 2 S 2 O 8 , ammonium persulfate] for a certain time to have various molecular weights, as well as various organic solvents such as formic acid, 1-methyl-2-pyrrolidinone (NMP ), Dimethyl sulfoxide (DMSO), N, N' -dimethylformamide (DMF), o -chlorophenol, m -cresol, tetrahydrofuran (THF), acetic acid, trifluoroacetic acid, chloroform, dichloromethane, benzene Soluble polypyrrole with excellent solubility It was.
본 발명의 방법에 의해 제조된 높은 가용성의, 높은 분자량을 갖는 폴리피롤의 분자량 측정 결과를 도 2에 나타내었다.The molecular weight measurement results of the high soluble, high molecular weight polypyrrole produced by the method of the present invention are shown in FIG. 2.
폴리피롤의 경우, 도판트가 도핑되지 않은, 중성상태의 폴리피롤 분자량을 측정하여야 폴리피롤 자체의 사슬길이를 추정할 수 있다. 그러나 도판트가 도핑된상태에서의 폴리피롤 분자량을 측정한 후 이로부터 중성상태의 폴리피롤 자체의 분자량을 다음의 가정을 통하여 계산할 수 있다. 일반적으로 전도성폴리피롤은 피롤 단량체 3∼4개당 도판트 하나가 도핑된 구조를 갖는것으로 알려져있다. 본 발명에서는 폴리피롤의 분자량 계산시 100% 도핑된 폴리피롤의 경우 피롤 단량체 3개당 도판트 하나가 도핑된 구조를 갖는것으로 가정하였다.In the case of polypyrrole, the chain length of the polypyrrole itself can be estimated by measuring the molecular weight of the polypyrrole in the neutral state, which is not doped with the dopant. However, after measuring the polypyrrole molecular weight in the doped state, the molecular weight of the polypyrrole itself in the neutral state can be calculated based on the following assumptions. In general, it is known that the conductive polypyrrole has a structure doped with one dopant per 3 to 4 pyrrole monomers. In the present invention, the polypyrrole is 100% doped polypyrrole in the calculation of the molecular weight of the polypyrrole was assumed to have a doped structure per three pyrrole monomers.
본 발명에 기인한 폴리피롤의 경우 디(2-에틸헥실)설폰에이트 이온이 도핑된 폴리피롤의 무게평균분자량(Mw)이 도 2에 나타낸바와 같이 174,756를 나타내었다. 피롤 단량체 3개의 분자량이 195, counter ion인 디(2-에틸헥실)설폰에이트의 분자량이 421 로 계산하면 디(2-에틸헥실)설폰에이트가 도핑된 3개의 피롤 단위의 분자량은 616로 계산된다. 이 결과로 부터, 디(2-에틸헥실)설폰에이트 이온이 도핑되지 않은, 중성상태의 폴리피롤 자체 분자량은 55,320 정도로 확인되었다. (174,756 x 195/616 = 55,320) 이는 본 발명에서 사용한 합성법에 의해 합성된 폴리피롤의 사슬길이가 약 851개의 피롤링에 해당함을 나타내고 있다.In the case of the polypyrrole due to the present invention, the weight average molecular weight (Mw) of the polypyrrole doped with di (2-ethylhexyl) sulfonate ion was 174,756 as shown in FIG. The molecular weight of three pyrrole units doped with di (2-ethylhexyl) sulfonate is calculated to be 616 when the molecular weight of the di (2-ethylhexyl) sulfonate having a molecular weight of 195 and a counter ion of 195 and a counter ion is 421. . From this result, the molecular weight of the polypyrrole itself in the neutral state, which was not doped with di (2-ethylhexyl) sulfonate ion, was found to be about 55,320. (174,756 x 195/616 = 55,320) This indicates that the chain length of polypyrrole synthesized by the synthesis method used in the present invention corresponds to about 851 pyrolling.
본 발명에서 화학적으로 제조된, 가용성 폴리피롤의 구조를 확인하기 위하여 제조된 폴리피롤 분말의 FT-IR 스펙트럼측정 결과, 1750cm-1의 C=O 진동 밴드(vibration band), 1580cm-1의 C=C 신축진동 밴드(stretching vibration), 1470, 1370cm-1의 C-N, C-C 진동 밴드(vibration band), 1230, 1080cm-1의 C-H 평면내 밴드(in plane band), 940cm-1의 C-H 평면외 밴드(out of plane band), 1117cm-1의 SO3 -의 진동밴드(vibration band)를 나타내어 일반식 II에 나타낸 바와 같이 음이온이 도핑된 폴리피롤이 합성되었음을 확인하였다(도 3 참조).FT-IR spectrum measurement results of the polypyrrole powders prepared in order to confirm the structure of chemically manufactured, a soluble polypyrrole in the present invention, C = O vibration band of 1750cm -1 (vibration band), C = C stretching of 1580cm -1 vibration band (stretching vibration), 1470, 1370cm -1 of CN, CC-band vibration (vibration band), 1230, CH plane of 1080cm -1 in the band (in plane band), CH out-of-plane band of 940cm -1 (out of plane band), and a vibration band of SO 3 − of 1117 cm −1 to confirm that anion-doped polypyrrole was synthesized as shown in Formula II (see FIG. 3).
이하에서는 본 발명의 방법에 따라, 다양한 유기용매에 가용성인, 다양한 분자량의 전도성 폴리피롤 합성방법을 구체적으로 설명하기로 한다.Hereinafter, according to the method of the present invention, a method for synthesizing conductive polypyrrole of various molecular weight, which is soluble in various organic solvents, will be described in detail.
실시예 1Example 1
본 발명품인 여러 유기용매에 가용성인, 다양한 분자량을 갖는 전도성 폴리피롤의 합성법은 다음과 같다.Synthesis of conductive polypyrrole having various molecular weights, soluble in various organic solvents of the present invention is as follows.
단량체인 피롤은 진공증류에 의해 정제시킨 후 사용하였고, 산화제인 과황산암모늄은 그대로 사용하였으며, 디(2-에틸헥실)설포숙신산은 디(2-에틸헥실)설포숙신산의 나트륨염을 화학처리하여 사용하였다.Pyrrole as a monomer was purified by vacuum distillation, and ammonium persulfate as an oxidizing agent was used as it was. Di (2-ethylhexyl) sulfosuccinic acid was chemically treated with sodium salt of di (2-ethylhexyl) sulfosuccinic acid. Used.
0℃에서 0.4 mol의 피롤과 0.2 mol의 디2-에틸헥실설포숙신산을 500㎖ 비이커내의 400㎖ 증류수에 넣어 자석 젓개로 저어준다. 이와 별도로 과황산암모늄 (0.2 ∼ 0.4mol 등)을 500㎖ 비이커내의 100㎖ 증류수에 넣어 자석 젓개로 저어준다. 0 ℃에서 과황산암모늄 용액을 피롤단량체와 디(2-에틸헥실)설포숙신산의 혼합물에 첨가한다 (투여시간 : 5초 ∼ 60분). 반응물을 자석 젓개로 서서히 저어주며 방치한다 (반응시간 : 30분 ∼ 72시간).0.4 mol pyrrole and 0.2 mol di2-ethylhexylsulfosuccinic acid were added to 400 ml distilled water in a 500 ml beaker at 0 ° C. and stirred with a magnetic stirrer. Separately, ammonium persulfate (0.2 to 0.4 mol, etc.) is added to 100 ml distilled water in a 500 ml beaker and stirred with a magnetic spoon. At 0 ° C., ammonium persulfate solution is added to the mixture of pyrrole monomer and di (2-ethylhexyl) sulfosuccinic acid (administration time: 5 seconds to 60 minutes). Stir the reaction slowly with a magnetic paddle (reaction time: 30 minutes to 72 hours).
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기내에서 증류수로 여과하며 세척하고, 여과후 얻어진 조각을 진공 라인과 연결된 건조관(drying tube)에 넣어 24시간동안 동적진공상태 (dynamic vacuum, 10-3torr)하에 건조하였다.After the reaction, the reaction solution was washed with distilled water in a Buchner funnel, washed, and the obtained pieces were placed in a drying tube connected to a vacuum line for 24 hours. 10 -3 torr).
제조된 폴리피롤의 GPC 측정결과로 부터 계산된 중성상태의 폴리피롤의 무게평균분자량은 3,000에서 35,000 사이로 나타났다.The weight average molecular weight of the polypyrrole in the neutral state calculated from the GPC measurement of the prepared polypyrrole was between 3,000 and 35,000.
도판트로 디(2-에틸헥실)설포숙신산의 나트륨염을 사용시에도 동일한 방법에 의해 합성하였다.The sodium salt of di (2-ethylhexyl) sulfosuccinic acid as dopantro was synthesized by the same method.
실시예 1에 제조된 폴리피롤을 알코올류에 녹인 용액으로 부터 용액 캐스팅(solution casting) 방법에 의해 제조된 폴리피롤 필름은 전기화학적 합성에 의하여 얻어진 필름과 비교시 손색없는 양질로 나타났다. 여러 가지 알코올 용매내에서 제조된 폴리피롤 용액들에 대하여 300∼2600nm의 파장 영역에서 측정된 UV/Vis-NIR 스펙트럼을 도 4에 나타내었다.The polypyrrole film prepared by the solution casting method from the solution of the polypyrrole prepared in Example 1 in alcohols appeared in good quality compared with the film obtained by electrochemical synthesis. The UV / Vis-NIR spectrum measured in the wavelength range of 300 to 2600 nm for the polypyrrole solutions prepared in various alcohol solvents is shown in FIG. 4.
근 적외선 영역에서의 UV/Vis-NIR 측정 결과t-부틸알코올(ε=12.5), 올레일 알코올(oleyl alcohol) 등 극성이 강하지 않은 알코올 등에서 free carrier tail 현상을 볼 수 있었다. 그러나 극성이 증가하는 1-부탄올 (ε=17.51), 이소부틸 알코올(ε=17.9) 등의 용매에서는 근적외선 영역에서 free carrier tail 현상이 감소하는 경향을 보였으며, 극성이 강한 2,2,2-트리플루오로에탄올(trifluoro ethanol), 에틸알코올(ε=24.5) 등의 용매에서는 free carrier tail 현상이 관찰되지 않았다.UV / Vis-NIR measurement in the near infrared region showed free carrier tail phenomenon in non-polar alcohols such as t -butyl alcohol (ε = 12.5) and oleyl alcohol. However, solvents such as 1-butanol (ε = 17.51) and isobutyl alcohol (ε = 17.9), which have increased polarity, tended to decrease the free carrier tail phenomenon in the near-infrared region. Free carrier tails were not observed in solvents such as trifluoroethanol and ethyl alcohol (ε = 24.5).
실시예 1에 의해 제조된 가용성 폴리피롤의 여러 용매에 대한 용해도 및 이들 용매에 녹인 용액으로부터 제조한 필름의 전기전도도를 표 1에 나타내었다.The solubility of the soluble polypyrrole prepared in Example 1 in the various solvents and the electrical conductivity of the films prepared from the solutions dissolved in these solvents are shown in Table 1.
표 1. 여러 유기용매에 대한 폴리피롤 분말의 용해도 및 제조된Table 1. Solubility and prepared polypyrrole powder in various organic solvents
폴리피롤 필름의 전기전도도Electrical Conductivity of Polypyrrole Film
실시예 2Example 2
0℃에서 0.4 mol의 피롤과 0.2 mol의 디(2-에틸헥실)설포숙신산을 500㎖ 비이커내의 400㎖ 증류수에 넣어 자석 젓개로 저어준다. 이와 별도로 과황산암모늄 0.1mol(혹은 0.05 mol∼0.4mol)을 500㎖ 비이커내의 100㎖ 증류수에 넣어 자석 젓개로 저어준다. 0 ℃에서 과황산암모늄 용액을 피롤단량체와 디(2-에틸헥실)설포숙신산의 혼합물에 첨가하고 (투여시간 : 5초 ∼ 60분), 일정시간(10분∼30분) 후 과황산암모늄 0.1 mol(혹은 0.05 mol∼0.4mol)을 첨가하였다 (투여시간 : 5초 ∼ 60분). 반응물을 자석 젓개로 서서히 저어주며 방치한다 (반응시간 : 30분 ∼ 84시간).0.4 mol pyrrole and 0.2 mol di (2-ethylhexyl) sulfosuccinic acid are added to 400 ml distilled water in a 500 ml beaker at 0 ° C. and stirred with a magnetic stirrer. Separately, 0.1 mol (or 0.05 mol to 0.4 mol) of ammonium persulfate is added to 100 ml distilled water in a 500 ml beaker and stirred with a magnetic paddle. Ammonium persulfate solution was added to a mixture of pyrrole monomer and di (2-ethylhexyl) sulfosuccinic acid at 0 ° C. (administration time: 5 seconds to 60 minutes), and after a certain time (10 minutes to 30 minutes), ammonium persulfate 0.1 mol (or 0.05 mol to 0.4 mol) was added (dosing time: 5 seconds to 60 minutes). Stir the reaction slowly with a magnetic paddle (reaction time: 30 minutes to 84 hours).
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기내에서 증류수로 여과하며 세척하고, 여과후 얻어진 조각을 진공 라인과 연결된 건조관(drying tube)에 넣어 24시간동안 동적진공상태(dynamic vacuum, 10-3torr)하에 건조시켰다.After the reaction is completed, the reaction solution is washed with distilled water in a Buchner funnel, washed, and the resulting pieces are placed in a drying tube connected to a vacuum line for 24 hours. 10 -3 torr).
이들 용액으로부터 캐스팅된 유연성있는 필름의 측정된 전기전도도는 사용된 용매에 따라 10-2∼ 20 S/cm의 값을 나타내었고 제조된 폴리피롤의 GPC 측정결과로 부터 계산된 중성상태의 폴리피롤의 무게평균분자량은 15,000에서 55,000 사이를 나타내었다.The measured electrical conductivity of the flexible films cast from these solutions showed a value of 10 -2 to 20 S / cm depending on the solvent used and the weight average of the polypyrrole in neutral state calculated from the GPC measurement of the prepared polypyrrole Molecular weights ranged from 15,000 to 55,000.
실시예 3Example 3
0℃에서 0.4 mol의 피롤과 0.2 mol의 디(2-에틸헥실)설퍼숙신산을 500㎖ 비이커내의 400㎖ 증류수에 넣어 자석 젓개로 저어준다. 이와 별도로 과황산암모늄 (0.2 ∼ 0.4mol 등)을 500㎖ 비이커내의 100㎖ 증류수에 넣어 자석 젓개로 저어준다. 0 ℃에서 과황산암모늄 용액 일부를 피롤단량체와 디(2-에틸헥실)설포숙신산의 혼합물에 첨가하고 (투여시간 : 5초 ∼ 60분), 일정시간 (10분∼30분) 후 과황산암모늄 용액 일부를 첨가하였다 (투여시간 : 5초 ∼ 60분). 일정시간 (10분∼30분) 후 과황산암모늄 용액의 남은 부분을 서서히(투여시간 : 5초 ∼ 60분) 첨가하여 총 3회에 걸쳐 산화제를 첨가하였다. 이와 같은 과황산암모늄(0.2 ∼ 0.4mol 등)의 첨가는 일정시간 (10분∼30분) 경과후 마다 총 양의 1/2 ∼1/5을 혼합물에 첨가하여(투여시간 : 5초 ∼ 60분) 총 2회∼5회에 걸쳐 나누어 첨가하였다. 반응물은 자석 젓개로 서서히 저어주며 방치한다 (반응시간 : 30분 ∼ 84시간).At 0 ° C, 0.4 mol pyrrole and 0.2 mol di (2-ethylhexyl) sulfuric acid are added to 400 ml distilled water in a 500 ml beaker and stirred with a magnetic stirrer. Separately, ammonium persulfate (0.2 to 0.4 mol, etc.) is added to 100 ml distilled water in a 500 ml beaker and stirred with a magnetic spoon. A portion of ammonium persulfate solution was added to the mixture of pyrrole monomer and di (2-ethylhexyl) sulfosuccinic acid at 0 ° C (administration time: 5 seconds to 60 minutes), and after a certain time (10 minutes to 30 minutes) ammonium persulfate A part of the solution was added (dosing time: 5 seconds to 60 minutes). After a certain time (10 minutes to 30 minutes), the remaining portion of the ammonium persulfate solution was slowly added (dosing time: 5 seconds to 60 minutes) to add an oxidant three times in total. Such addition of ammonium persulfate (0.2 to 0.4 mol, etc.) is performed by adding 1/2 to 1/5 of the total amount to the mixture after a predetermined time (10 minutes to 30 minutes) (administration time: 5 seconds to 60 minutes). Min) added in portions over 2-5 times in total. The reaction is left to stir with a magnetic stir slowly (reaction time: 30 minutes to 84 hours).
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기에서 증류수로 세척하며 여과하고, 여과후 얻어진 조각을 진공 라인과 연결된 건조관(drying tube)에 넣어 24시간동안 동적진공상태(dynamic vacuum, 10-3torr)하에 건조하였다.After the reaction was completed, the reaction solution was washed with distilled water in a Buchner funnel, filtered, and the obtained pieces were placed in a drying tube connected to a vacuum line for 24 hours. -3 torr).
이들 용액으로부터 캐스팅된 유연성있는 필름의 측정된 전기전도도는 사용된 용매에 따라 10-2∼35 S/cm의 값을 나타내었고, 제조된 폴리피롤의 GPC 측정결과로 부터 계산된 중성상태의 폴리피롤의 무게평균분자량은 25,000에서 70,000 사이를 나타내었다.The measured electrical conductivity of the flexible films cast from these solutions showed values of 10 −2 to 35 S / cm depending on the solvent used, and the weight of the neutral polypyrrole calculated from the GPC measurement of the prepared polypyrrole Average molecular weights ranged from 25,000 to 70,000.
실시예 4Example 4
실시예 1과 동일한 조건에서 0℃에서 0.4 mol의 피롤치환체 [일반식 Ⅰ에서 R이 수소, 탄소 1개∼탄소 20개의 알킬(alkyl), 이소오알킬(isoalkyl), 알콕시(alkoxy), 알콕시알킬(alkoxyalkyl), 알킬설퍼닐 (alkylsulfonyl), 알콕시카보닐(alkoxycarbonyl), 알킬실란(alkylsilane), 아릴설퍼닐(arylsulfonyl), 알케닐(alkenyl), R'가 수소, 탄소 1개∼탄소 20개의 알킬(alkyl), 이소오알킬(isoalkyl), 알콕시(alkoxyl), 알콕시알킬(alkoxyalkyl), 알킬설퍼닐(alkylsulfonyl), 알콕시카보닐(alkoxycarbonyl), 알킬실란 (alkylsilane), 아릴설퍼닐(arylsulfonyl), 알케닐(alkenyl), X가 수소, 탄소 1개∼탄소 10개의 알킬(alkyl), 이소오알킬(isoalkyl), 알콕시(alkoxy), 알콕시알킬(alkoxyalkyl), 알킬설퍼닐 (alkylsulfonyl), 알콕시카보닐(alkoxycarbonyl), 알킬실란(alkylsilane), 아릴설퍼닐(arylsulfonyl), 알케닐(alkenyl) 인 것을 특징]와 0.2 mol의 디(2-에틸헥실)설포숙신산 혹은 디(2-에틸헥실)설포숙신산의 나트륨염을 도판트로 사용하여 폴리피롤을 제조한다.0.4 mol of pyrrole substituent at 0 ° C. under the same conditions as in Example 1 [In Formula I, R is hydrogen, alkyl of 1 to 20 carbons, isoalkyl, alkoxy, alkoxyalkyl. (alkoxyalkyl), alkylsulfonyl, alkoxycarbonyl, alkylsilane, arylsulfonyl, alkenyl, R 'is hydrogen, C1-C20 alkyl alkyl, isoalkyl, alkoxy, alkoxyalkyl, alkoxyalkyl, alkylsulfonyl, alkoxycarbonyl, alkylsilane, arylsulfonyl, al Alkenyl, X is hydrogen, alkyl of 1 to 10 carbons, isoalkyl, alkoxy, alkoxyalkyl, alkylsulfonyl, alkoxycarbonyl ( alkoxycarbonyl, alkylsilane, arylsulfonyl, alkenyl] and 0.2 mol di (2-ethylhexyl) sulfo Polypyrrole is prepared using the sodium salt of succinic acid or di (2-ethylhexyl) sulfosuccinic acid as a dopant.
실시예 5Example 5
실시예 1과 동일한 조건에서 0℃에서 0.4 mol의 피롤과 0.2 mol의 도판트[일반식 Ⅳ에서 R이 탄소 2개∼탄소 20개의 알킬(alkyl), 이소오알킬(isoalkyl), 알콕시(alkoxy), 알콕시알킬(alkoxyalkyl), 알킬술포닐(alkylsulfonyl), 알콕시카보닐(alkoxycarbonyl), 알킬실란(alkylsilane), 아릴술포닐(arylsulfonyl), 알케닐(alkenyl), R'가 수소, 탄소 2개∼탄소 20개의 알킬(alkyl), 이소오알킬(isoalkyl), 알콕실(alkoxy), 알콕시알킬(alkoxyalkyl), 알킬술포닐(alkylsulfonyl), 알콕시카보닐(alkoxycarbonyl), 알킬실란(alkylsilane), 아릴술포닐(arylsulfonyl), 알케닐(alkenyl), X가 설폰에이트(sulfonate), 카르복실에이트(carboxylate), 포스페이트(phosphate)인 것이 특징]를 사용하여 가용성, 전도성 폴리피롤을 제조한다.0.4 mol pyrrole and 0.2 mol dopant at R < 0 > C under the same conditions as in Example 1 [In Formula IV, R is 2 to 20 carbon alkyl, isoalkyl, alkoxy , Alkoxyalkyl, alkylsulfonyl, alkoxycarbonyl, alkylsilane, arylsulfonyl, alkenyl, R 'is hydrogen, carbon 2 to carbon 20 alkyl, isoalkyl, alkoxy, alkoxyalkyl, alkoxyalkyl, alkylsulfonyl, alkoxycarbonyl, alkylsilane, arylsulfonyl ( arylsulfonyl, alkenyl, X is sulfonate (sulfonate), carboxylate, phosphate, characterized in that the soluble, conductive polypyrrole is prepared.
(Ⅳ)(Ⅳ)
실시예 6Example 6
실시예 1과 동일한 방법으로 중합을 실시하되, 0.1 mol의 디(2-에틸헥실)설포숙신산 혹은 디(2-에틸헥실)설포숙신산의 나트륨염과 0.1 mol의 방향족술폰산(benzenesulfonic acid, toluenesulfonic acid, sulfosalicylic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthol-amino-disulfonic acid, anthraquinonesulfonic acid, anthraquinonedisulfonic acid, etc.)을 각각 혼합한 혼합도판트를 사용하여 가용성 폴리피롤을 제조하였다.The polymerization was carried out in the same manner as in Example 1 except that sodium salt of 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid or di (2-ethylhexyl) sulfosuccinic acid and 0.1 mol of aromaticsulfonic acid (benzenesulfonic acid, toluenesulfonic acid, Soluble polypyrrole was prepared using a mixed dopant of sulfosalicylic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthol-amino-disulfonic acid, anthraquinonesulfonic acid, anthraquinonedisulfonic acid, etc.).
반응이 끝난 후, 반응 용액을 부흐너(Buchner) 깔때기에서 증류수로 세척하며 여과하고, 여과후 얻어진 조각을 진공 라인과 연결된 건조관(drying tube)에 넣어 24시간동안 동적진공상태(dynamic vacuum, 10-3torr)하에 건조하였다. 건조된 분말의 다양한 유기용매에 대한 용해도는 3 ∼ 7 wt./wt.%로 나타났다. 이들 용액으로부터 캐스팅된 유연성있는 필름의 측정된 전기전도도는 사용된 용매에 따라 10-2∼ 30 S/cm의 값을 나타내었다.After the reaction was completed, the reaction solution was washed with distilled water in a Buchner funnel, filtered, and the obtained pieces were placed in a drying tube connected to a vacuum line for 24 hours. -3 torr). The solubility of the dried powder in various organic solvents was found to be 3-7 wt./wt.%. The measured electrical conductivity of the flexible films cast from these solutions showed values of 10 −2 to 30 S / cm depending on the solvent used.
실시예 7Example 7
실시예 1과 동일한 방법으로 중합을 실시하되, 0.1 mol의 디(2-에틸헥실)설포숙신산 혹은 디(2-에틸헥실)설포숙신산의 나트륨염과 0.1 mol의 방향족술폰산의 나트륨염 (benzenesulfonic acid sodium salt, toluenesulfonic acid sodium salt, sulfosalicylic acid sodium salt, naphthalenesulfonic acid sodium salt, naphthalenedisulfonic acid sodium salt, naphthol-amino-disulfonic acid sodiumsalt, anthraquinonesulfonic acid sodium salt, anthraquinone disulfonic acid sodium salt, etc.)을 각각 혼합한 혼합도판트를 사용하여 가용성 폴리피롤을 제조한다The polymerization was carried out in the same manner as in Example 1 except that sodium salt of 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid or di (2-ethylhexyl) sulfosuccinic acid and 0.1 mol of aromatic sulfonic acid (benzenesulfonic acid sodium salt, toluenesulfonic acid sodium salt, sulfosalicylic acid sodium salt, naphthalenesulfonic acid sodium salt, naphthalenedisulfonic acid sodium salt, naphthol-amino-disulfonic acid sodium salt, anthraquinonesulfonic acid sodium salt, anthraquinone disulfonic acid sodium salt, etc.) The soluble polypyrrole using
실시예 8Example 8
실시예 1과 동일한 방법으로 중합을 실시하되, 0.1 mol의 디(2-에틸헥실)설포숙신산 혹은 디(2-에틸헥실)설포숙신산의 나트륨염과 0.1 mol의 방향족카르복실산 및 그의 염(benzenecarboxylic acid, benzenecarboxylic acid sodium salt, toluenecarboxylic acid, toluenecarboxylic acid sodium salt, naphthalenecarboxylic acid, naphthalenecarboxylic acid sodium salt, anthraquinone carboxylic acid, anthraquinonecarboxylic acid sodium salt, etc.)을 각각 혼합한 혼합도판트를 사용하여 가용성 폴리피롤을 제조한다The polymerization was carried out in the same manner as in Example 1 except that sodium salt of 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid or di (2-ethylhexyl) sulfosuccinic acid and 0.1 mol of aromatic carboxylic acid and salts thereof (benzenecarboxylic Soluble polypyrrole is prepared using a mixed dopant mixed with acid, benzenecarboxylic acid sodium salt, toluenecarboxylic acid, toluenecarboxylic acid sodium salt, naphthalenecarboxylic acid, naphthalenecarboxylic acid sodium salt, anthraquinone carboxylic acid, anthraquinonecarboxylic acid sodium salt, etc.).
실시예 9Example 9
실시예 1과 동일한 방법으로 중합반응을 실시하되, 0.1 mol의 디(2-에틸헥실)설포숙신산 혹은 디(2-에틸헥실)설포숙신산 나트륨염과 0.1 mol의 방향족포스포닉산, 포스포릭산(benzenephosphonic acid, benzenephosphonic acid sodium salt, toluenephosphonic acid, toluenephosphonic acid sodium salt, naphthalenephosphonic acid, naphthalenephosphonic acid sodium salt, anthraquinone phosphonic acid, anthraquinonephosphonic acid sodium salt, benzenephosphoric acid, benzenephosphoric acid sodium salt, toluenephosphoric acid, toluenephosphoric acid sodium salt, naphthalenephosphoric acid,naphthalenephosphoric acid sodium salt, anthraquinone phosphoric acid, anthraquinone phosphoric acid sodium salt, etc.)을 각각 혼합한 혼합도판트를 사용하여 가용성 폴리피롤을 제조한다The polymerization was carried out in the same manner as in Example 1 except that 0.1 mol of di (2-ethylhexyl) sulfosuccinic acid or di (2-ethylhexyl) sulfosuccinic acid sodium salt, 0.1 mol of aromatic phosphonic acid and phosphoric acid ( benzenephosphonic acid, benzenephosphonic acid sodium salt, toluenephosphonic acid, toluenephosphonic acid sodium salt, naphthalenephosphonic acid, naphthalenephosphonic acid sodium salt, anthraquinone phosphonic acid, anthraquinonephosphonic acid sodium salt, benzenephosphoric acid, benzenephosphoric acid sodium salt, toluenephosphoric acid, toluenephosphicic acid Soluble polypyrrole is prepared by using a mixed dopant mixed with acid, naphthalenephosphoric acid sodium salt, anthraquinone phosphoric acid, anthraquinone phosphoric acid sodium salt, etc.).
실시예 10Example 10
실시예 1과 동일한 방법으로 중합을 수행하되, 각각 0.1 mol의 황산암모늄철(ferrous ammonium sulfate), 황산철(ferric sulfate), 과염소산철(ferric perchlorate), 과망간산칼륨(potassium permanganate), 2크롬산칼륨(potassium dichromate) 등을 산화제로서 사용하여 가용성 폴리피롤을 제조하였다.The polymerization was carried out in the same manner as in Example 1, except that 0.1 mol of ferrous ammonium sulfate, ferric sulfate, ferric perchlorate, potassium permanganate, and potassium dichromate ( soluble polypyrrole was prepared using potassium dichromate) and the like as an oxidizing agent.
또한 산화제인 과황산암모늄(ammonium persulfate) 0.5 mol과 각각 0.5 mol의 산화제들 [황산암모늄철(ferrous ammonium sulfate), 황산철(ferric sulfate), 과염소산철(ferric perchlorate), 과망간산칼륨 (potassium permanganate), 2크롬산칼륨(potassium dichromate)등]을 혼합한 혼합산화제를 사용하여 가용성 폴리피롤을 제조하였다.In addition, 0.5 mol of ammonium persulfate as an oxidizing agent and 0.5 mol of oxidizing agents (ferrous ammonium sulfate, ferric sulfate, ferric perchlorate, potassium permanganate, and potassium permanganate, respectively) Soluble polypyrrole was prepared using a mixed oxidant mixed with potassium dichromate (potassium dichromate, etc.).
제조된 폴리피롤을 1-부탄올, 이소프로필 알코올, 이소부틸알코올, 벤질알코올, 2,2,2-트리플루오로 에탄올, 1-메틸-2-피롤리돈(NMP), 디메틸술폭시드 (DMSO),N,N'-디메틸포름아미드 (DMF),o-클로로페놀,m-크레졸, 테트라히드로푸란 (THF), 클로로포름, 디클로로메탄 등의 용매에 녹여 매끈한 표면의 유연성있는 필름을 제조할 수 있었다.Polypyrrole prepared was 1-butanol, isopropyl alcohol, isobutyl alcohol, benzyl alcohol, 2,2,2-trifluoro ethanol, 1-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), A smooth surface flexible film was prepared by dissolving in a solvent such as N, N' -dimethylformamide (DMF), o -chlorophenol, m -cresol, tetrahydrofuran (THF), chloroform and dichloromethane.
이들 용액으로 부터 캐스팅된 free standing film의 측정된 전기전도도는 사용된 용매에 따라 10-2∼ 10 S/cm의 값을 나타내었다.The measured electrical conductivity of the free standing films cast from these solutions ranged from 10 -2 to 10 S / cm depending on the solvent used.
실시예 11Example 11
실시예 2와 동일한 방법으로 중합을 수행하되, 각각 0.1 mol의 산화제 [황산암모늄철(ferrous ammonium sulfate), 황산철(ferric sulfate), 과염소산철(ferric perchlorate), 과망간산칼륨(potassium permanganate), 중크롬산칼륨(potassium dichromate)등]을 사용하여 가용성 폴리피롤을 제조하였다. 또한 산화제로 0.5 mol의 과황산암모늄과 각각 0.5mol의 산화제 [황산암모늄철(ferrous ammonium sulfate), 황산철(ferric sulfate), 과염소산철(ferric perchlorate), 과망간산칼륨(potassium permanganate), 2크롬산칼륨(potassium dichromate) 등]를 혼합하여 가용성 폴리피롤을 제조하였다.The polymerization was carried out in the same manner as in Example 2, except that 0.1 mol of an oxidizing agent (ferrous ammonium sulfate, ferric sulfate, ferric perchlorate, potassium permanganate, potassium dichromate, respectively) was used. (potassium dichromate), etc., to prepare soluble polypyrrole. In addition, 0.5 mol of ammonium persulfate and 0.5 mol of oxidizing agent (ferrous ammonium sulfate, ferric sulfate, ferric perchlorate, potassium permanganate, potassium dichromate) potassium dichromate) and the like] to prepare a soluble polypyrrole.
제조된 폴리피롤을 1-부탄올, 이소프로필 알코올, 이소부틸알코올, 벤질알코올, 2,2,2-트리플루오로 에탄올, 1-메틸-2-피롤리디논(NMP), 디메틸술폭시드 (DMSO),N,N'-디메틸포름아미드 (DMF),o-클로로페놀,m-크레졸, 테트라히드로푸란 (THF), 클로로포름, 디클로로메탄 등의 용매에 녹여 매끈한 표면의 free standing film을 제조할 수 있었다.The polypyrrole prepared was 1-butanol, isopropyl alcohol, isobutyl alcohol, benzyl alcohol, 2,2,2-trifluoro ethanol, 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), A smooth standing free standing film was prepared by dissolving in a solvent such as N, N' -dimethylformamide (DMF), o -chlorophenol, m -cresol, tetrahydrofuran (THF), chloroform, dichloromethane, and the like.
이들 용액으로부터 캐스팅된 유연성있는 필름의 측정된 전기전도도는 사용된 용매에 따라 10-2∼ 20 S/cm의 값을 나타내었다.The measured electrical conductivity of the flexible films cast from these solutions showed values of 10 −2 to 20 S / cm depending on the solvent used.
실시예 12Example 12
실시예 1와 동일한 방법으로 중합을 수행하되, 중합시 용매가 유기용매[알콜류(부탄올, 메탄올 등) 클로로포름, 다이클로로메탄, 아세트로나이트릴, 포름산, 아세트산 등)]에서 제조되거나 물과 유기용매의 혼합용매에 의해 합성반응 온도(-30℃에서 상온)를 달리하여 합성되어 가용성, 전도성 폴리피롤의 제조방법이 제공된다.The polymerization was carried out in the same manner as in Example 1, in which the solvent was prepared in an organic solvent (alcohol (butanol, methanol, etc.) chloroform, dichloromethane, acetonitrile, formic acid, acetic acid, etc.) or water and an organic solvent. Synthesized by varying the synthesis reaction temperature (-30 ℃ at room temperature) by a mixed solvent of is provided a method for producing a soluble, conductive polypyrrole.
본 발명은 여러 유기용매에 가용성인, 다양한 분자량의 전도성 폴리피롤을 제조함으로써 가공성에 따른 작업성의 향상을 가능케 할 뿐 아니라, 기존의 금속에 비해 다양한 기계적특성, 가격적인 경쟁력을 가지며, 다양한 형태로의 적용이 가능하게 되어 관련 산업체에 많은, 직접적인 영향을 미치리라 생각된다. 본 발명품인 가용성, 전도성 폴리피롤은 정전기방지, 전자기파흡수체, 전자기파차폐용 코팅재료 및 전도성도료 개발, 축전지, photoelectrochemical 전지, electrochromic display, 부식방지용 도료, 투명전도성전극, capacitor용 고분자전해질, metallization, resistive heating, cable shielding, microwave absorbor, 온도, 충격, 화학적 센서, nano fiber, optical transducer 등으로의 응용이 가능하다.The present invention not only enables the improvement of workability according to workability by preparing conductive polypyrroles having various molecular weights, which are soluble in various organic solvents, but also have various mechanical properties and cost competitiveness over existing metals, and are applied in various forms. It is thought that this will be possible and will have many, direct impacts on the industry involved. Soluble, conductive polypyrrole is an antistatic, electromagnetic wave absorber, electromagnetic wave shielding coating material and conductive paint development, storage battery, photoelectrochemical cell, electrochromic display, corrosion preventing paint, transparent conductive electrode, polymer electrolyte for capacitor, metallization, resistive heating, Applications include cable shielding, microwave absorbers, temperature, shock, chemical sensors, nano fiber and optical transducers.
Claims (18)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000031719A KR20010112574A (en) | 2000-06-09 | 2000-06-09 | Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight |
| PCT/KR2001/000982 WO2002010251A1 (en) | 2000-06-09 | 2001-06-09 | Method for making polypyrrole |
| AU64353/01A AU6435301A (en) | 2000-06-09 | 2001-06-09 | Method for making polypyrrole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000031719A KR20010112574A (en) | 2000-06-09 | 2000-06-09 | Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20010112574A true KR20010112574A (en) | 2001-12-20 |
Family
ID=19671530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020000031719A KR20010112574A (en) | 2000-06-09 | 2000-06-09 | Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20010112574A (en) |
| AU (1) | AU6435301A (en) |
| WO (1) | WO2002010251A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100437198B1 (en) * | 2001-02-23 | 2004-06-23 | 장관식 | Water Soluble Polypyrrole with High Solubility and Method for Preparation thereof |
| KR100684034B1 (en) * | 2002-05-15 | 2007-02-16 | 이종영 | Composition of the conductive polymer, and manufacture method thereof |
| WO2009091184A2 (en) | 2008-01-17 | 2009-07-23 | Soluble conductive polymer and method for preparing same | |
| CN113713782A (en) * | 2021-08-16 | 2021-11-30 | 中化学朗正环保科技有限公司 | Silver @ polypyrrole composite material for wastewater adsorption and preparation method and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101143664B1 (en) * | 2003-11-28 | 2012-05-09 | 이데미쓰 고산 가부시키가이샤 | Conductive polyaniline composition, process for producing the same, and molded object thereof |
| CN101893595A (en) * | 2010-06-25 | 2010-11-24 | 中国农业大学 | Chemically modified electrode, preparation thereof and method for rapid determination of acid value of plant oil |
| CN114621463B (en) * | 2022-03-25 | 2023-07-28 | 武汉工程大学 | Polyurethane polypyrrole composite gel with compressive sensing performance and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0352920A (en) * | 1989-07-19 | 1991-03-07 | Matsushita Electric Ind Co Ltd | Electroconductive polymer, production thereof and electrolytic capacitor using same polymer |
| JPH05217808A (en) * | 1992-02-05 | 1993-08-27 | Fujitsu Ltd | Solid electrolytic capacitor and its manufacture |
| KR0162864B1 (en) * | 1995-01-19 | 1999-01-15 | 김은영 | Process for preparing electrically conductive polypyrrole having excellent solubility |
| KR20000006968A (en) * | 1999-11-16 | 2000-02-07 | 장관식 | Method for preparation of solubility polypyrrole electrolyte |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2819679B2 (en) * | 1989-10-06 | 1998-10-30 | 日本曹達株式会社 | Method for producing conductive polypyrrole solution |
| KR20000001140A (en) * | 1998-06-09 | 2000-01-15 | 권호택 | Process for producing polypyrrole |
| KR100318153B1 (en) * | 1999-06-09 | 2001-12-22 | 오응주 | Method for Preparation of the Conductive Polypyrrole having a high Solubility in Alcohol and Various Organic Solvents |
-
2000
- 2000-06-09 KR KR1020000031719A patent/KR20010112574A/en active Search and Examination
-
2001
- 2001-06-09 AU AU64353/01A patent/AU6435301A/en not_active Abandoned
- 2001-06-09 WO PCT/KR2001/000982 patent/WO2002010251A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0352920A (en) * | 1989-07-19 | 1991-03-07 | Matsushita Electric Ind Co Ltd | Electroconductive polymer, production thereof and electrolytic capacitor using same polymer |
| JPH05217808A (en) * | 1992-02-05 | 1993-08-27 | Fujitsu Ltd | Solid electrolytic capacitor and its manufacture |
| KR0162864B1 (en) * | 1995-01-19 | 1999-01-15 | 김은영 | Process for preparing electrically conductive polypyrrole having excellent solubility |
| KR20000006968A (en) * | 1999-11-16 | 2000-02-07 | 장관식 | Method for preparation of solubility polypyrrole electrolyte |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100437198B1 (en) * | 2001-02-23 | 2004-06-23 | 장관식 | Water Soluble Polypyrrole with High Solubility and Method for Preparation thereof |
| KR100684034B1 (en) * | 2002-05-15 | 2007-02-16 | 이종영 | Composition of the conductive polymer, and manufacture method thereof |
| WO2009091184A2 (en) | 2008-01-17 | 2009-07-23 | Soluble conductive polymer and method for preparing same | |
| US9284453B2 (en) | 2008-01-17 | 2016-03-15 | Sung-Joon Lee | Soluble conductive polymer and method for preparing same |
| CN113713782A (en) * | 2021-08-16 | 2021-11-30 | 中化学朗正环保科技有限公司 | Silver @ polypyrrole composite material for wastewater adsorption and preparation method and application thereof |
| CN113713782B (en) * | 2021-08-16 | 2024-02-06 | 中化学朗正环保科技有限公司 | Silver@polypyrrole composite material for wastewater adsorption and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6435301A (en) | 2002-02-13 |
| WO2002010251A1 (en) | 2002-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4518440B2 (en) | Use of neutral compounds | |
| US7053174B2 (en) | Polythiophenes | |
| JP4974095B2 (en) | Method for producing water-soluble π-conjugated polymer | |
| EP0804497B1 (en) | Soluble, electroconductive polypyrrole and method for preparing the same | |
| WO2007066353A2 (en) | Novel polymers of 3,4-propylenedioxythiophene derivatives with pendant functional groups | |
| JP6040615B2 (en) | Thiophene compound, water-soluble conductive polymer and aqueous solution thereof, and production method thereof | |
| KR20010112574A (en) | Method for preparation of Polypyrrole having a solubility in various organic solvents and various molecular weight | |
| JPH0425309B2 (en) | ||
| KR100242220B1 (en) | Electrically conductive alternating copolymer and method of preparing such a copolymer | |
| KR100374719B1 (en) | Method for Preparation of the Soluble Poly(3,4-ethylenedioxythiophene) Powder | |
| US8613611B2 (en) | Electrically conductive polyrotaxane | |
| JP2000204158A (en) | Aromatic amine derivative and soluble conductive compounds | |
| JP2601207B2 (en) | Method for producing conductive polymer molded article | |
| KR100318153B1 (en) | Method for Preparation of the Conductive Polypyrrole having a high Solubility in Alcohol and Various Organic Solvents | |
| US6822069B2 (en) | Poly (5-aminoquinoxalines) and use thereof | |
| JPH0574467A (en) | Macromolecular solid electrolyte | |
| Rao et al. | Studies on biphenyl disulphonic acid doped polyanilines: Synthesis, characterization and electrochemistry | |
| JPH0813873B2 (en) | Water-soluble self-doped conductive polymer and method for producing the same | |
| JP3058735B2 (en) | Polypyrrole derivative and method for producing the same | |
| JP3164671B2 (en) | Arylene vinylene polymer and method for producing the same | |
| JP3334111B2 (en) | Manufacturing method of conductive polymer film | |
| US5162470A (en) | Polymers with electrical and nonlinear optical properties | |
| US5498477A (en) | N-phenylhydroxylamine polymers, and associated methods of preparation and use | |
| JP2982088B2 (en) | Method for producing polyaniline derivative | |
| JP2576403B2 (en) | Conductive polymer compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| N231 | Notification of change of applicant |