KR100373926B1 - Rapid Synthesis of High Molecular Weight Polyaniline - Google Patents

Rapid Synthesis of High Molecular Weight Polyaniline Download PDF

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KR100373926B1
KR100373926B1 KR10-2000-0055318A KR20000055318A KR100373926B1 KR 100373926 B1 KR100373926 B1 KR 100373926B1 KR 20000055318 A KR20000055318 A KR 20000055318A KR 100373926 B1 KR100373926 B1 KR 100373926B1
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polyaniline
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이성주
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스마트텍 주식회사
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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/16—Halogen-containing compounds

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Abstract

본 발명은 전도성 고분자 폴리아닐린의 합성법에 관한 것으로 더욱 상세하게는 폴리아닐린의 합성에 있어서 염화리튬 등의 빙점강하제를 사용하지 않고 인산을 사용하여 고분자량의 폴리아닐린(Mw=200,000 이상)을 제조하는 방법에 관한 것이다.The present invention relates to a method for synthesizing conductive polymer polyaniline, and more particularly, to a method for preparing a high molecular weight polyaniline (Mw = 200,000 or more) using phosphoric acid without the use of a freezing-lowering agent such as lithium chloride in the synthesis of polyaniline. will be.

이를 위하여 본 발명은 폴리아닐린의 합성에 있어서 기존에 사용하던 강산인 염산과 황산 대신에 일반적으로 사용되지 않는 약산인 인산을 사용하였고 반응시간 단축을 위하여 촉매제로 염화리튬, 염화철(Ⅲ) 등의 염을 소량 사용하였고, 합성에 소요되는 반응시간을 5시간 이내 단축하여 고분자량의 폴리아닐린을 합성하는 특징이 있다.To this end, the present invention uses hydrochloric acid and phosphoric acid, which is not generally used in the synthesis of polyaniline, instead of sulfuric acid, which is conventionally used, and salts such as lithium chloride and iron (III) chloride as catalysts to shorten the reaction time. A small amount was used, and the reaction time required for synthesis was shortened within 5 hours to synthesize high molecular weight polyaniline.

Description

고분자량 폴리아닐린의 신속 합성 방법{Rapid Synthesis of High Molecular Weight Polyaniline}Rapid Synthesis of High Molecular Weight Polyaniline

본 발명은 고분자량을 가지는 폴리아닐린의 신속합성법에 관한 것으로 더욱 상세하게는 폴리아닐린의 합성에 있어서 염화리튬 등의 빙점강하제를 사용하지 않고 인산을 사용하여 고분자량의 폴리아닐린(Mw=200,000 이상)을 제조하는 방법에 관한 것이다.The present invention relates to a rapid synthesis method of polyaniline having a high molecular weight. More specifically, in the synthesis of polyaniline, a high molecular weight polyaniline (Mw = 200,000 or more) is prepared by using phosphoric acid without using a freezing point lowering agent such as lithium chloride. It is about a method.

최초의 폴리아닐린의 합성에 관한 보고는 1826년 Unverdorber에 의해 인디고(indigo)를 건식 증류한 것이다. 그후 여러 가지 합성법이 보고되어져 있으나 가장 일반적인 합성법은 염산과 황산 등의 강산성 수용액에서 산화제를 사용하여 아닐린 단량체(monomer)를 중합하여 만드는 것이다. 그러나 0℃에서 합성한 폴리아닐린의 경우 분자량(Mw=53,000)이 낮아 기계적 성질이 매우 약한 단점을 가지고 있으며 0℃이하의 온도에서 합성하고자 할 때에는 산 용액이 얼어버리는 단점이 있었다.The first report on the synthesis of polyaniline was dry distillation of indigo by Unverdorber in 1826. Since then, various synthetic methods have been reported, but the most common method is to polymerize aniline monomers using an oxidizing agent in strong acidic solutions such as hydrochloric acid and sulfuric acid. However, in the case of polyaniline synthesized at 0 ° C., the molecular weight (Mw = 53,000) has a low weakness in mechanical properties, and the acid solution freezes when synthesized at a temperature below 0 ° C.

Mattoso 등의 연구(Synth. Metal 1994, 68, 1)에는 고분자량(Mw=440,000)의 폴리아닐린의 합성의 경우 1M염산 용액에 빙점강하제로 염화리튬을 가하여 5.8M염/염산수용액이 되게 하고, -40℃에서 산화제인 (NH4)2S2O8을 가하여 48시간동안 반응시키는 것으로 반응시간이 매우 길고 고가의 염화리튬을 사용하는 등 많은 문제점을 가지고 있다.In Mattoso et al. (Synth. Metal 1994, 68, 1), the synthesis of high molecular weight (Mw = 440,000) polyaniline was added to a 1M hydrochloric acid solution by adding lithium chloride as a freezing point lowering agent to 5.8 M salt / hydrochloric acid solution. It is reacted for 48 hours by adding (NH 4) 2 S 2 O 8, which is an oxidizing agent at 40 ° C., and has many problems such as using a long reaction time and using expensive lithium chloride.

이상과 같이 기존의 폴리아닐린의 합성법은 Mw=200,000 이상 가지는 고분자량의 경우 매우 낮은 온도에서 장시간 반응시켜야하고, 0℃ 근처의 낮은 온도에서 합성하고자하는 경우에는 비교적 빠른 시간 내에 합성은 가능하지만 분자량이 적어 가공 후 폴리아닐린의 기계적 성질이 떨어지는 단점을 가지고 있다.As described above, the conventional method of synthesizing polyaniline should be reacted at a very low temperature for a long time in the case of a high molecular weight having Mw = 200,000 or more. The mechanical properties of polyaniline are poor after processing.

본 발명은 상기와 같은 문제점을 해소하기 위하여 폴리아닐린의 합성에 있어서 기존에 사용하던 강산인 염산과 황산 대신에 일반적으로 사용되지 않는 약산인 인산을 사용하였다. 이산은 수분함량에 따라 -80℃이하에서도 얼지 않는 특성을 가지고 있다. 따라서 별도의 빙점강하제를 첨가하지 않고 -80℃이하의 온도에서도 폴리아닐린의 합성이 가능하게된다. 또한 합성시 폴리아닐린의 분자량에 영향을 주는 인자인 산화제를 한방울씩 서서히 가하면서 분자량 증가를 가져올 수 있으며, 또한 반응시간 단축을 위하여 촉매제로 염화리튬, 염화철(Ⅲ) 등의 염을 소량 사용하였고, 합성에 소요되는 반응시간을 5시간 이내 단축하여 고분자량의 폴리아닐린을 합성하는 특징이 있다.In the present invention, in order to solve the above problems, in the synthesis of polyaniline, hydrochloric acid and sulfuric acid, which are generally not used, are used instead of hydrochloric acid and sulfuric acid, which are conventionally used. Diacids do not freeze even below -80 ℃ depending on moisture content. Therefore, it is possible to synthesize polyaniline even at a temperature below -80 ° C without adding an additional freezing agent. In addition, the molecular weight can be increased by gradually adding an oxidant, which is a factor affecting the molecular weight of polyaniline, drop by drop, and a small amount of salts such as lithium chloride and iron (III) chloride are used as a catalyst to shorten the reaction time. The reaction time required to shorten within 5 hours is characterized by the synthesis of high molecular weight polyaniline.

도1은 인산수용액에서 합성한 시료의 X-선 회절도이다. 기존의 폴리아닐린 시료와 비교하여 결정도가 매우 크게 나타남을 확인할 수 있다.1 is an X-ray diffraction diagram of a sample synthesized in an aqueous phosphate solution. It can be seen that the crystallinity is very large compared to the conventional polyaniline sample.

도2는 인산수용액의 상평형도이다. 인산의 조성이 약 63%에서 빙점이 최저임을 알 수 있다.2 is a phase equilibrium diagram of an aqueous phosphate solution. It can be seen that the freezing point is lowest at about 63% of the phosphoric acid composition.

본 발명은 빙점강하제를 사용하지 않고 인산의 수분 함량에 따라 합성온도를 선택적으로 조절하여 사용할 수 있다. 인산은 아닐린의 질소자리에 결합하여 반응속도를 서서히 조절하여줌으로서 보다 고분자량의 폴리아닐린을 합성할 수 있고 도1에서 보는 바와 같이 이때 얻어진 폴리아닐린은 1M염산 수용액에서 합성한 시료보다도 더 큰 결정성을 가지는 특질이 있다. 도2는 인산의 상평형도 이다. 인산의 양이 증가하고 수분의 양이 감소함에 따라 빙점은 급격히 떨어지고 약 63w%에서는 빙점이 -80℃이하를 나타냄으로 인산을 사용하여서는 -80℃까지 폴리아닐린의 합성이 가능하다.The present invention can be used by selectively controlling the synthesis temperature according to the moisture content of phosphoric acid without using a freezing point depressant. Phosphoric acid binds to the nitrogen site of aniline and gradually adjusts the reaction rate to synthesize polyaniline of higher molecular weight. As shown in FIG. 1, polyaniline obtained at this time has greater crystallinity than the sample synthesized in 1M hydrochloric acid solution. Eggplants have characteristics. 2 is a phase diagram of phosphoric acid. As the amount of phosphoric acid increases and the amount of water decreases, the freezing point drops sharply, and the freezing point is about -80 ° C or less at about 63w%. Thus, polyaniline can be synthesized up to -80 ° C using phosphoric acid.

본 발명에서는 이를 비교하고자 다음과 같은 실험을 수행하였다. 각각의 합성법에 의한 폴리아닐린의 분자량은 표1에서 보는 봐와 같다. 표1에 수록된 GPC(Gel Permeation Chromatography) 분석 결과에서 인산을 이용하면 손쉽게 고분자량의 폴리아닐린을 합성 할 수 있다.In the present invention, the following experiment was performed to compare the results. The molecular weight of polyaniline by each synthesis method is as shown in Table 1. In the results of gel permeation chromatography (GPC) analysis shown in Table 1, it is possible to easily synthesize high molecular weight polyaniline using phosphoric acid.

실시 예1.상온에서 1M 염산수용액을 이용한 폴리아닐린 합성 Example 1. Polyaniline Synthesis Using 1M Hydrochloric Acid Solution at Room Temperature

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 60분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기(Buchner funnel)로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료1-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 60 minutes of synthesis time while maintaining the reaction temperature. After the reaction time, the precipitate was filtered using a decompression apparatus using a Buchner funnel with a filter paper until the filtrate was cleared with 1M hydrochloric acid solution. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 1-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 60분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료1-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 60 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 1-2).

실시 예2.0℃에서 1M 염산수용액을 이용한 폴리아닐린 합성 Example 2. Polyaniline Synthesis Using 1M Aqueous Hydrochloric Acid at 0 ℃

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹여 0℃을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료2-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 90 minutes of synthesis time while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 2-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹여 0℃를 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료2-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 90 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 2-2).

실시 예3.-10℃, 염산수용액 하에서 폴리아닐린 합성 Example 3. Synthesis of polyaniline under aqueous solution at -10 ° C

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹이고 빙점 강하제로 LiCl 5.8M을 가하여 녹인 후 -10℃를 유지하였다. 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹이고 빙점강하제 LiCl 5.8M을 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 2분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료3-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid, and dissolved with LiCl 5.8 M as a freezing point depressant, and maintained at -10 ° C. 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid and 5.8 M of the ice-lowering agent, LiCl 5.8 M, were kept at -10 ° C. When the temperature of both solutions reaches -10 ° C, the solution containing the oxidant is magnetically stirred in the solution containing the aniline and the oxidant is added for 2 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 3-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 염산 600ml에 녹이고 빙점 강하제로 LiCl 5.8M을 가하여 녹인 후 -10℃를 유지하였다. 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산에 녹이고 빙점강하제 LiCl 5.8M을 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 한방울씩 가하여 100분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료3-2)을 합성 하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M hydrochloric acid, and dissolved with LiCl 5.8 M as a freezing point depressant, and maintained at -10 ° C. 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M hydrochloric acid and 5.8 M of the ice-lowering agent, LiCl 5.8 M, were kept at -10 ° C. When the temperature of the two solutions reaches -10 ° C, the solution containing the oxidant is added to the solution containing aniline by magnetic stirring and dropwise adds the oxidant over 100 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered and dried using a vacuum pump to synthesize polyaniline (sample 3-2).

실시 예4.상온에서 황산수용액을 이용한 폴리아닐린 합성 Example 4. Polyaniline Synthesis Using Sulfate Aqueous Solution at Room Temperature

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M의 황산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 60분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료4-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M sulfuric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 60 minutes of synthesis time while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 4-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M의 황산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 60분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료4-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M sulfuric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 60 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 4-2).

실시 예5.0℃에서 황산수용액을 이용한 폴리아닐린 합성 Example 5. Polyaniline Synthesis Using Sulfate Aqueous Solution at 0 ℃

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M의 황산에 녹여 0℃를 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료5-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M sulfuric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 90 minutes of synthesis time while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 5-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M의 황산에 녹여 0℃를 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료5-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1 M sulfuric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 90 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 5-2).

실시 예6.-10℃, 황산수용액 하에서 폴리아닐린 합성 Example 6. Synthesis of Polyaniline under Aqueous Sulfate Solution at -10 ℃

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹이고 빙점강하제 LiCl 5.8M을 가하여 녹인 후 -10℃를 유지하였다. 23g의 산화제 (NH4)2S2O8을 400ml의 1M 황산에 녹이고 빙점 강하제 LiCl 5.8M을 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 2분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료6-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid and dissolved by adding a melting point reducing agent, LiCl 5.8 M, and then maintained at -10 ° C. 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1M sulfuric acid, and the freezing point depressant LiCl 5.8M was dissolved to maintain -10 ° C. When the temperature of both solutions reaches -10 ° C, the solution containing the oxidant is magnetically stirred in the solution containing the aniline and the oxidant is added for 2 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 6-1).

40ml(0.22mol)의 정제한 아닐린을 1M의 황산 600ml에 녹이고 빙점강하제 LiCl 5.8M을 가하여 녹인 후 -10℃를 유지하였다. 23g의 산화제 (NH4)2S2O8을 400ml의 1M 황산에 녹이고 빙점 강하제 LiCl 5.8M을 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 한방울씩 가하여 100분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료6-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 1 M sulfuric acid and dissolved by adding a melting point reducing agent, LiCl 5.8 M, and then maintained at -10 ° C. 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 1M sulfuric acid, and the freezing point depressant LiCl 5.8M was dissolved to maintain -10 ° C. When the temperature of the two solutions reaches -10 ° C, the solution containing the oxidant is added to the solution containing aniline by magnetic stirring and dropwise adds the oxidant over 100 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 6-2).

실시 예7.상온에서 인산수용액을 이용한 폴리아닐린 합성 Example 7. Synthesis of Polyaniline Using Aqueous Phosphate Solution at Room Temperature

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료7-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 90 minutes of synthesis time while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 7-1).

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 실온을 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 실온을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 90분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름 종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료7-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain room temperature, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain room temperature. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 90 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered with a Buchner funnel using a decompression device and filtered through a 1 M hydrochloric acid solution using a filter paper until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 7-2).

실시 예8.0℃에서 인산수용액을 이용한 폴리아닐린 합성 Example 8. Synthesis of Polyaniline Using Aqueous Phosphate at 0 ° C

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 0℃를 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 2분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 합성시간 180분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료8-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidant to the solution containing the aniline with a magnetic paddle and add the oxidant over two minutes. The reaction is stirred for 180 minutes of synthesis time while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 8-1).

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 0℃를 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석젓개로 저어주며 한방울씩 가하여 100분간 산화제를 넣어준다. 산화제를 전부 가한 후 반응물을 반응 온도를 유지하면서 반응시간 180분 동안 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과하였다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료8-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain 0 ° C. When the temperature of the two solutions reaches equilibrium, stir the solution containing the oxidizing agent to the solution containing the aniline with a magnetic paddle and add one drop by drop to add the oxidizing agent for 100 minutes. After adding all the oxidants, the reaction was stirred for 180 minutes while maintaining the reaction temperature. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 8-2).

실시 예9.-10℃, 인산수용액 하에서 폴리아닐린 합성 Example 9. Synthesis of Polyaniline under Aqueous Phosphate Solution at -10 ℃

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 -10℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 2분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료9-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain -10 ° C, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain -10 ° C. . When the temperature of both solutions reaches -10 ° C, the solution containing the oxidant is magnetically stirred in the solution containing the aniline and the oxidant is added for 2 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05 M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 9-1).

40ml(0.22mol)의 정제한 아닐린을 62.7%의 인산 600ml에 녹여 -10℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 62.7%의 인산에 녹여 -10℃를 유지하였다. 두 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 한방울씩 가하여 100분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 -10℃를 유지하면서 24시간 교반한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료9-2)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid to maintain -10 ° C, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of 62.7% phosphoric acid to maintain -10 ° C. . When the temperature of the two solutions reaches -10 ° C, the solution containing the oxidant is added to the solution containing aniline by magnetic stirring and dropwise adds the oxidant over 100 minutes. The reaction is stirred for 24 hours while maintaining -10 ° C. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 9-2).

실시 예10.-10℃, 인산수용액 하에서 폴리아닐린 합성 Example 10. Synthesis of Polyaniline under Aqueous Phosphate Solution at -10 ℃

(촉매제로 소량의 염화리튬 첨가)(Add small amount of lithium chloride as catalyst)

40ml(0.22mol)의 정제한 아닐린을 1%의 염화리튬을 첨가한 62.7%의 인산 600ml에 녹여 -10℃를 유지하고 23g의 산화제 (NH4)2S2O8을 1%의 염화리튬을 첨가한 400ml의 62.7%의 인산에 녹여 -10℃를 유지한다. 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 2분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 교반하며 -10℃를 유지하면서 5시간 반응하여 합성한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료10-1)을 합성하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid added with 1% lithium chloride to maintain -10 ° C, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added with 1% lithium chloride. Dissolve in 400 ml of 62.7% phosphoric acid added and maintain -10 ° C. When the temperature of the solution reaches -10 ° C, the solution containing the oxidant is magnetically stirred in the solution containing the aniline and the oxidant is added over 2 minutes. The reaction is continuously stirred and reacted for 5 hours while maintaining at -10 ° C to synthesize. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 10-1).

40ml(0.22mol)의 정제한 아닐린을 1%의 염화리튬을 첨가한 62.7%의 인산 600ml에 녹여 -10℃를 유지하고 23g의 산화제 (NH4)2S2O8을 1%의 염화리튬을 첨가한 400ml의 62.7%의 인산에 녹여 -10℃를 유지한다. 용액의 온도가 -10℃에 도달하면 산화제가 포함된 용액을 아닐린이 포함된 용액에 자석 교반하여 한방울씩 100분에 걸쳐 산화제를 넣어준다. 반응물을 계속해서 교반하며 -10℃를 유지하면서 5시간 교반하여 합성한다. 반응 시간이 지난 후 침전물을 감압장치를 이용하여 뷰흐너 깔때기로 거름종이를 사용하여 1M의 염산 용액으로 여과액이 맑아질 때까지 여과하였다. 걸러진 여과물을 다시 1ℓ의 1M 염산 용액에 넣어 15시간 교반한 후 다시 여과한다. 0.05M의 NH4OH 용액을 넣고 15시간 교반한 후 여과하고 진공펌프를 사용하여 건조하여 폴리아닐린(시료10-2)을 합성하였다.실시 예11.GPC 분석합성된 폴리아닐린을 0.5% LiCl/NMP (wt/vol) 용액에 녹여서 GPC를 사용하여 분자량을 측정하였다. 이 때 이동상의 유속은 0.8ml/min이고 Styragel HT3, Styragel HT4, Styragel HT6E 컬럼을 사용했으며 컬럼의 온도는 100℃, 검출기의 온도는 50℃이고 기준물질로 Polystyrene을 사용하였다.40 ml (0.22 mol) of purified aniline was dissolved in 600 ml of 62.7% phosphoric acid added with 1% lithium chloride to maintain -10 ° C, and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 Dissolve in 400 ml of 62.7% phosphoric acid added and maintain -10 ° C. When the temperature of the solution reaches -10 ° C, the solution containing the oxidant is magnetically stirred in the solution containing the aniline, and the oxidant is added drop by drop over 100 minutes. The reaction is continuously stirred and maintained at −10 ° C. for 5 hours to synthesize. After the reaction time was passed, the precipitate was filtered using a decompression device with a Buchner funnel using a filter paper with 1M hydrochloric acid solution until the filtrate was clear. The filtered filtrate was put back into 1 L of 1M hydrochloric acid solution, stirred for 15 hours, and filtered again. 0.05M NH 4 OH solution was added thereto, stirred for 15 hours, filtered, and dried using a vacuum pump to synthesize polyaniline (sample 10-2). Example 11. GPC analysis The synthesized polyaniline was dissolved in 0.5% LiCl / NMP (wt / vol) solution to determine molecular weight using GPC. At this time, the flow rate of the mobile phase was 0.8ml / min, Styragel HT3, Styragel HT4, Styragel HT6E column was used, the column temperature is 100 ℃, detector temperature is 50 ℃, polystyrene was used as a reference material.

이상에서 상술한 바와같이 본 발명은 인산수용액을 사용하여 손쉽게 고분자량의 폴리아닐린을 합성함으로서 빠른 시간내에 저렴한 비용으로 기계적 성질이 우수한 폴리아닐린을 합성할 수 있다.As described above, the present invention can synthesize polyaniline having excellent mechanical properties at low cost in a short time by easily synthesizing high molecular weight polyaniline using an aqueous phosphate solution.

Claims (4)

빙점강하제를 사용하지 않고 -5℃ 이하의 온도에서 인산 함량이 20wt%에서 80wt% 사이의 인산 수용액을 사용하여 Mw 값이 150,000 이상의 고분자량을 가지는 폴리아닐린의 합성방법Synthesis method of polyaniline having a high molecular weight of 150,000 or more using a phosphoric acid aqueous solution having a phosphoric acid content of 20wt% to 80wt% at a temperature below -5 ° C without using a freezing point depressant 반응속도를 빠르게 하기 위하여 청구항1의 조건에 촉매제로 소량(1wt% 이내)의 염화리튬을 사용하는 방법Method of using a small amount (less than 1wt%) of lithium chloride as a catalyst under the conditions of claim 1 to speed up the reaction rate 촉매제로 염화리튬 대신에 염화철(Ⅲ) 또는 염화칼슘 또는 염화나트륨을 사용하는 방법Method of using iron (III) chloride or calcium chloride or sodium chloride as a catalyst instead of lithium chloride 삭제delete
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KR930008032A (en) * 1991-10-08 1993-05-20 리챠드 에이지. 쥬브 Products of Inherently Conductive Polymers and Thermoplastic Mixtures and Methods for Making the Same
KR940003986A (en) * 1992-08-11 1994-03-14 타파니 알호 Conductive plastic material and manufacturing method thereof
JPH0892542A (en) * 1994-09-27 1996-04-09 Nitto Denko Corp Electrically conductive composition and electrically conductive tape using the same
JPH10168329A (en) * 1993-03-03 1998-06-23 Internatl Business Mach Corp <Ibm> Water-soluble conductive polymer composition, its production and utilization

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KR930008032A (en) * 1991-10-08 1993-05-20 리챠드 에이지. 쥬브 Products of Inherently Conductive Polymers and Thermoplastic Mixtures and Methods for Making the Same
KR940003986A (en) * 1992-08-11 1994-03-14 타파니 알호 Conductive plastic material and manufacturing method thereof
KR100238809B1 (en) * 1992-08-11 2000-01-15 티파니 알로 Conducting plastics material and a method for its preparation
JPH10168329A (en) * 1993-03-03 1998-06-23 Internatl Business Mach Corp <Ibm> Water-soluble conductive polymer composition, its production and utilization
JPH0892542A (en) * 1994-09-27 1996-04-09 Nitto Denko Corp Electrically conductive composition and electrically conductive tape using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009091184A2 (en) 2008-01-17 2009-07-23 Soluble conductive polymer and method for preparing same

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