KR100276266B1 - Method for producing polypyrrole that maintains solubility for a long time - Google Patents
Method for producing polypyrrole that maintains solubility for a long time Download PDFInfo
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- KR100276266B1 KR100276266B1 KR1019980024143A KR19980024143A KR100276266B1 KR 100276266 B1 KR100276266 B1 KR 100276266B1 KR 1019980024143 A KR1019980024143 A KR 1019980024143A KR 19980024143 A KR19980024143 A KR 19980024143A KR 100276266 B1 KR100276266 B1 KR 100276266B1
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Abstract
본 발명은 가용성 폴리피롤의 제조방법에 관한 것이며; 그 목적은 세척공정을 개선하므로써 1개월이상 가용성을 유지시킬 수 있는 폴리피롤의 제조방법을 제공함에 있다.The present invention relates to a process for preparing soluble polypyrrole; The object is to provide a method for producing polypyrrole that can be maintained for more than one month by improving the cleaning process.
상기 목적 달성을 위한 본 발명은 5-고리 복소환 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하여 중합하고, 이 중합된 용액을 유기용매로 적어도 1회이상 -15~10℃의 저온에서 세척하여 감압여과하는 것을 포함하여 구성되는 가용성 폴리피롤의 제조방법에 관한 것을 그 기술적 요지로 한다.The present invention for achieving the above object is polymerized by dropping an oxidizing agent in an aqueous solution in which a 5-ring heterocyclic pyrrole monomer and a dopant are dissolved, and washing the polymerized solution at least once with an organic solvent at a low temperature of -15 to 10 ° C. The technical gist of the present invention relates to a method for producing soluble polypyrrole comprising filtration under reduced pressure.
Description
본 발명은 가용성 폴리피롤의 제조에 관한 것으로서, 보다 상세하게는 세척공정을 개선하므로써 1개월이상 가용성을 유지시킬 수 있는 폴리피롤의 제조방법에 관한 것이다.The present invention relates to the production of soluble polypyrrole, and more particularly, to a method for producing polypyrrole that can be maintained for more than one month by improving the washing process.
폴리피롤(polypyrrole)은 완전히 환원된 상태에서는 거의 전기를 통하지 않으나, 사슬의 일부가 산화제에 의해서 산화되거나 전기화학적으로 산화되면 전기를 통할 수 있게 되며, 이러한 특성으로 폴리피롤은 전기전도성 코팅재료 또는 전극재료 등으로 사용된다. 상기 폴리피롤은 화학적 또는 전기화학적으로 합성될 수 있는데, 화학적으로 합성되는 경우에는 검은 분말 형태로 얻을 수 있고, 전기화학적으로 합성될 때에는 필림형태로도 얻을 수 있다. 그러나, 대부분의 전도성 고분자이 불용, 불융인 특성을 갖는 것과 마찬가지로 기존의 합성된 폴리피롤도 일반 유기용매에 대해 불용, 불융인 특성을 갖음에 따라 그 응용에 많은 제약이 있어왔다.Polypyrrole is almost not electricity when fully reduced, but when part of the chain is oxidized or electrochemically oxidized by an oxidizing agent, the polypyrrole is electrically conductive coating material or electrode material, etc. Used as The polypyrrole may be synthesized chemically or electrochemically. When chemically synthesized, the polypyrrole may be obtained in the form of a black powder, and in the case of the electrochemical synthesis, it may also be obtained in the form of a film. However, as most conductive polymers have insoluble and insoluble properties, conventional synthetic polypyrroles have many limitations in their applications as they have insoluble and insoluble properties with respect to general organic solvents.
하지만, 최근 대한민국 공개특허 제96-29367호에 개시된 기술에 의하면, 가용성을 나타내는 폴리피롤이 합성되어 그 응용에 있어 많은 가능성을 나타내게 되었다. 상기 대한민국 공개특허 제96-29367호는 가용 전기전도성 폴리피롤의 제조방법에 대한 기술로서, 5-고리 복소환 단량체인 피롤(pyrrole)을 수용액상에서 도데실벤젠술폰산(dodecylbenzenesulfonic acid; DBSA)을 도판트(dopant)로, 그리고 암모늄퍼술페이트를 산화제로 사용하여 폴리피롤을 중합시키는 방법이다.However, according to the technique disclosed in Korean Patent Laid-Open Publication No. 96-29367, polypyrrole exhibiting solubility has been synthesized and shows a great possibility in its application. Korean Patent Publication No. 96-29367 discloses a method for preparing a soluble electrically conductive polypyrrole, wherein a dodecylbenzenesulfonic acid (DBSA) is used as a dopyl (pyrrole), which is a 5-ring heterocyclic monomer, in an aqueous solution. dopant) and ammonium persulfate as oxidant to polymerize polypyrrole.
구체적으로 상기한 합성은 중합과정과 중합된 용액을 세척하는 공정으로 나뉘어 진다. 중합은 저온에서 피롤 단량체(pyrrole monomer)와 도판트를 물에 녹여 넣고, 산화제를 적하(dropping)시켜 교반시키면서 이루어지며, 중합된 용액의 세척은 메탄올, 아세톤과 같은 유기 용매와 증류수를 이용하여 미반응물, 올리고머(oligomer) 및 불순물을 제거시킴으로써 이루어진다. 이러한 과정을 거쳐서 중합된 폴리피롤 분말의 경우 클로로포름(chloroform), 또는 m-크레졸(m-cresol)과 같은 유기용매에는 가용성을 나타낸다.Specifically, the synthesis is divided into a polymerization process and a process of washing the polymerized solution. The polymerization is carried out by dissolving the pyrrole monomer and the dopant in water at a low temperature, dropping the oxidizing agent and stirring, and washing the polymerized solution using an organic solvent such as methanol and acetone and distilled water. By removing reactants, oligomers and impurities. Polypyrrole powder polymerized through this process is soluble in organic solvents such as chloroform or m-cresol.
한편, 폴리피롤이 가용성을 나타내기 위해서는 일정한 단량체와 산화제의 비율이상이 되어야 하고, 폴리피롤의 응용을 위해서는 가용성을 나타내는 성질이 계속 지속되어야만 한다. 그러나, 상기 가용성 폴리피롤의 합성기술에서는 가용성 향상에 대한 연구는 있었지만 합성된 폴리피롤의 가용성을 오랫동안 유지시킬 수 있는 폴리피롤의 제조에 대한 연구가 미진하여 폴리피롤 합성초기에 나타난 가용성이 오랜동안 유지되지 않아서 계속적인 응용에는 한계를 나타내었다.On the other hand, in order for polypyrrole to be soluble, the ratio of a monomer and an oxidizing agent must be higher than that, and for the application of polypyrrole, soluble property must be maintained. However, the synthesis of the soluble polypyrrole has been studied to improve the solubility, but studies on the preparation of polypyrrole that can maintain the solubility of the synthesized polypyrrole for a long time is insufficient, so the solubility at the beginning of the synthesis of polypyrrole was not maintained for a long time The application is limited.
따라서, 본 발명은 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하여 중합하고, 이 중합된 용액을 저온에서 감압세척하므로써 합성되는 폴리피롤의 초기에 나타나는 가용성을 오랫동안 유지할 수 있는 폴리피롤 제조방법을 제공함에 그 목적이 있다.Accordingly, the present invention provides a method for producing polypyrrole that can maintain a long period of solubility at the initial stage of polypyrrole synthesized by dropping an oxidizing agent into an aqueous solution in which a pyrrole monomer and a dopant are dissolved, and washing the polymerized solution under reduced pressure at a low temperature. Has its purpose.
상기 목적 달성을 위한 본 발명은 5-고리 복소환 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하는 중합공정과 이 중합된 용액을 세척하는 공정을 포함하여 구성되는 가용 전기전도성 폴리피롤의 제조방법에 있어서,The present invention for achieving the above object is a manufacturing method of a soluble electrically conductive polypyrrole comprising a polymerization step of dropping an oxidizing agent in an aqueous solution in which a 5-ring heterocyclic pyrrole monomer and a dopant are dissolved, and washing the polymerized solution. To
상기 중합된 용액을 유기용매로 적어도 1회이상 -15~10℃의 저온에서 세척하여 감압여과하는 것을 포함하여 구성되는 가용성 폴리피롤 제조방법에 관한 것이다.It relates to a method for producing soluble polypyrrole comprising washing the polymerized solution at least once with an organic solvent at a low temperature of −15˜10 ° C. and filtration under reduced pressure.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 5-고리 복소환 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하여 중합하고, 이 중합된 용액을 저온상태에서 세척하고 감압여과함에 특징이 있다. 이렇게 제조되는 전기전도성 폴리피롤은 일반 유기용매에 대해 가용성뿐만아니라 합성 초기의 가용성이 적어도 1개월이상 유지될 수 있다.The present invention is characterized by dropping and polymerizing an oxidizing agent in an aqueous solution in which a 5-ring heterocyclic pyrrole monomer and a dopant are dissolved, and washing the polymerized solution at low temperature and filtration under reduced pressure. The electrically conductive polypyrrole thus prepared may be maintained for at least one month at the initial stage of synthesis as well as solubility with respect to a general organic solvent.
본 발명은 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하는 중합공정과 이 중합된 용액을 세척하는 공정을 포함하여 구성되는 가용 전기전도성 폴리피롤의 제조에 매우 유용하다. 본 발명의 폴리피롤 제조는 기존의 도데실벤젠술폰산은 물론 옥틸벤젠술폰산(octylbenzenesulfonic acid) 또는 부틸벤젠술폰산(butylbenzenesulfonic acid)과 같이, n≥4이상인 알킬벤젠술폰산(alkylbenzenesulfonic acid; CnH2n+1C6H4SO3H)을 도판트로 하는 폴리피롤의 제조에도 적용이 가능하다. 또한, 본 발명의 경우 폴리피롤 중합에 사용되는 산화제로는 암모늄퍼술페이트[ammonium persulfate;(NH4)2S2O8], 염화제이철(FeCl3), 또는 과망간산칼륨(KMnO4) 등 다양한 산화제가 적용될 수 있다.The present invention is very useful for the production of soluble electrically conductive polypyrrole comprising a polymerization step of dropping an oxidant into an aqueous solution in which a pyrrole monomer and a dopant are dissolved, and a step of washing the polymerized solution. Polypyrrole preparation of the present invention, such as octylbenzenesulfonic acid (octylbenzenesulfonic acid) or butylbenzenesulfonic acid as well as conventional dodecylbenzenesulfonic acid, alkylbenzenesulfonic acid (alkylbenzenesulfonic acid; C n H 2n + 1 C) The present invention is also applicable to the production of polypyrrole having 6 H 4 SO 3 H) as a dopant. In the present invention, various oxidants such as ammonium persulfate (NH 4 ) 2 S 2 O 8 ], ferric chloride (FeCl 3 ), or potassium permanganate (KMnO 4 ) may be used as the oxidizing agent used in the polypyrrole polymerization. Can be applied.
본 발명은 상기 중합된 용액을 유기용매로 적어도 1회이상 -15~10℃의 저온에서 세척하여 감압여과하므로써 폴리피롤의 합성 초기 가용성을 적어도 1개월이상 그대로 유지할 수 있다.The present invention can maintain the initial solubility of polypyrrole as it is at least one month by washing the polymerized solution with an organic solvent at least one time at a low temperature of -15 ~ 10 ℃ at reduced pressure.
본 발명의 저온세척은 세척하는 동안 폴리피롤의 산화를 방지하고, 이에 따라 폴리피롤의 변성과 물성변화를 방지하여 폴리피롤 분말의 가용성을 오랫동안 유지할 수 있다. 저온세척시 그 온도는 -15~10℃의 범위가 바람직한데, 그 이유는 -15℃이하에서 세척하는 경우 교반에 어려움이 따르고, 10℃이상에서 세척하는 경우에는 가용성 분말의 저장성이 저하되기 때문이다. 보다 바람직하게는 용액의 세척을 -10~5℃의 온도에서 행하는 것이다.The low temperature washing of the present invention prevents oxidation of polypyrrole during washing, thereby preventing polypyrrole from being denatured and changing its physical properties, thereby maintaining the solubility of the polypyrrole powder for a long time. When washing at a low temperature, the temperature is preferably in the range of -15 to 10 ° C, because when washing below -15 ° C, it is difficult to stir, and when washing at 10 ° C or above, the storage capacity of the soluble powder is lowered. to be. More preferably, the solution is washed at a temperature of -10 to 5 ° C.
또 저온세척시 유기용매는 알콜계 또는 케톤계 유기용매를 사용함이 바람직하다. 알콜계 용매로는 예를들면, 메탄올, 에탄올, 프로판올, 부탄올 등 다양하게 적용되며, 또한 케톤계 용매로는 아세톤, 메틸에틸케톤 등을 이용할 수 있다. 상기 세척은 유기용매 대신 물을 사용하거나 유기용매와 물을 번갈아 사용하여 세척하거나 혹은 유기용매와 물을 혼용하여도 무방하다. 그러나, 저온세척은 적어도 1회이상 행함이 바람직한데, 이는 가능한 한 폴리피롤에 존재하는 불순물 등을 완전 제거하여 오랫동안 가용성을 확보하기 위함이다.In addition, it is preferable to use an alcohol solvent or a ketone organic solvent as the organic solvent at low temperature washing. As the alcohol solvent, for example, methanol, ethanol, propanol, butanol and the like are variously applied, and as the ketone solvent, acetone, methyl ethyl ketone and the like can be used. The washing may be performed by using water instead of the organic solvent, or alternately using the organic solvent and water, or may be mixed with the organic solvent and water. However, low temperature washing is preferably performed at least once, in order to ensure the long-term availability by completely removing impurities and the like present in the polypyrrole as much as possible.
이와같이 세척하여 감압여과한 다음, 건조된 폴리피롤 분말은 클로로포름(chloroform), 또는 m-크레졸(m-cresol) 등의 유기용매에 대해 적어도 1개월이상 가용성을 그대로 유지할 수 있어 저장성이 향상되기 때문에 그 응용분야가 매우 확장된다.After washing and filtration under reduced pressure in this manner, the dried polypyrrole powder can be maintained in the solubility for at least one month for organic solvents such as chloroform or m-cresol, thereby improving storage properties. The field is very broad.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
[실시예]EXAMPLE
종래예Conventional example
250㎖의 물에 피롤단량체와 도데실벤젠술폰산을 2:1의 몰비로 혼합한 수용액을 교반하면서 여기에 피롤단량체와 암모늄퍼술페이트를 6.5~7:1의 몰비로 첨가하여 중합시켰다. 중합된 용액에 약 700㎖의 알콜을 첨가하여 상온(18~25℃)에서 1회 여과한 다음, 물과 알콜을 사용하여 2회 번갈아 세척하여 여과한 후, 이를 건조하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 클로로포름에 용해하고, 분말의 가용상태를 관찰하였다.Pyrrole monomer and ammonium persulfate were added thereto in a molar ratio of 6.5-7: 1 and polymerized while stirring an aqueous solution in which pyrrole monomer and dodecylbenzenesulfonic acid were mixed in a molar ratio of 2: 1 in 250 ml of water. About 700 ml of alcohol was added to the polymerized solution, and the filtrate was filtered once at room temperature (18-25 ° C.), washed twice with water and alcohol, and filtered, and dried to obtain a polypyrrole powder. The powder thus prepared was dissolved in chloroform after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the solubility of the powder was observed.
그 결과 1주일 경과후 용해한 분말은 완전히 클로로포름에 녹았으나, 2주일 경과된 분말을 용해한 용액에는 일부 불용 분말이 존재하였고, 또 1개월 경과된 분말은 완전 불용상태임이 확인되었다.As a result, the powder dissolved after one week was completely dissolved in chloroform, but some insoluble powder was present in the solution in which the powder was dissolved for two weeks, and the powder after one month was completely insoluble.
비교예Comparative example
여과를 약 30~40℃에서 실시한 것을 제외하고는 종래예와 같이 하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 물에 용해하고, 분말의 가용상태를 관찰하였다.A polypyrrole powder was obtained in the same manner as in the conventional example except that the filtration was performed at about 30 to 40 ° C. The powder thus prepared was dissolved in water after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the availability of the powder was observed.
그 결과 2일, 1주일 경과된 분말은 일부 불용상태로 존재하였으며, 2주일 경과된 분말은 완전히 클로로포름에 녹지 않았음을 확인할 수 있었다.As a result, two days, one week after the powder was present in some insoluble state, it was confirmed that the two weeks after the powder was not completely dissolved in chloroform.
발명예1Inventive Example 1
종래예와 동일하게 중합된 용액을 700㎖의 알콜을 사용하여 10℃에서 감압여과하는 과정을 3회 실시한 다음, 건조하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 클로로포름에 용해하고, 분말의 가용상태를 관찰하였다.In the same manner as in the prior art, the polymerization solution was filtered three times under reduced pressure at 10 ° C. using 700 ml of alcohol, followed by drying to obtain polypyrrole powder. The powder thus prepared was dissolved in chloroform after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the solubility of the powder was observed.
그 결과 1개월후 용해한 분말도 완전히 클로로포름에 녹았으며, 2개월후 용해한 분말은 약간의 불용 분말이 존재하였다.As a result, the powder dissolved after 1 month was completely dissolved in chloroform, and the powder dissolved after 2 months had some insoluble powder.
발명예2Inventive Example 2
감압여과를 0℃에서 3회 실시한 것을 제외하고는 발명예1과 같이 하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 물에 용해하고, 분말의 가용상태를 관찰하였다.Polypyrrole powder was obtained in the same manner as in Example 1 except that the filtration under reduced pressure was performed three times at 0 ° C. The powder thus prepared was dissolved in water after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the availability of the powder was observed.
그 결과 2개월후에 용해한 분말까지도 완전히 클로로포름에 녹았음을 확인할 수 있었다.As a result, it was confirmed that even the powder dissolved after 2 months was completely dissolved in chloroform.
발명예3Inventive Example 3
감압여과를 -5℃에서 3회 실시한 것을 제외하고는 발명예1과 같이 하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 클로로포름에 용해하고, 분말의 가용상태를 관찰하였다.Polypyrrole powder was obtained in the same manner as in Example 1 except that the filtration under reduced pressure was performed three times at -5 ° C. The powder thus prepared was dissolved in chloroform after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the solubility of the powder was observed.
그 결과 2개월후에 용해한 분말까지도 완전히 클로로포름에 녹았음을 확인할 수 있었다.As a result, it was confirmed that even the powder dissolved after 2 months was completely dissolved in chloroform.
발명예4Inventive Example 4
도판트로서 옥틸벤젠술폰산을 사용한 것을 제외하고는 발명예2와 같이 하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 클로로포름에 용해하고, 분말의 가용상태를 관찰하였다.A polypyrrole powder was obtained in the same manner as in Example 2 except that octylbenzenesulfonic acid was used as the dopant. The powder thus prepared was dissolved in chloroform after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the solubility of the powder was observed.
그 결과 2개월후에 용해한 분말까지도 완전히 클로로포름에 녹았음을 확인할 수 있었다.As a result, it was confirmed that even the powder dissolved after 2 months was completely dissolved in chloroform.
발명예5Inventive Example 5
도판트로서 부틸벤젠술폰산을 사용한 것을 제외하고는 발명예2와 같이 하여 폴리피롤 분말을 얻었다. 이같이 제조된 분말을 각각 2일, 1주일, 2주일, 1개월, 2개월후 클로로포름에 용해하고, 분말의 가용상태를 관찰하였다.Polypyrrole powder was obtained in the same manner as in Example 2 except that butylbenzenesulfonic acid was used as the dopant. The powder thus prepared was dissolved in chloroform after 2 days, 1 week, 2 weeks, 1 month and 2 months, respectively, and the solubility of the powder was observed.
그 결과 2개월후에 용해한 분말까지도 완전히 클로로포름에 녹았음을 확인할 수 있었다.As a result, it was confirmed that even the powder dissolved after 2 months was completely dissolved in chloroform.
상술한 바와 같이, 본 발명은 피롤단량체와 도판트가 용해된 수용액에 산화제를 적하하여 중합하고, 이 중합된 용액을 저온에서 세척후 감압여과하므로써 합성된 폴리피롤 분말의 초기에 나타나는 가용성을 오랫동안 유지할 수 있어 저장성이 더욱 향상되고 이에 따라 폴리피롤의 응용분야를 더욱 확대하는 매우 유용한 효과가 있다.As described above, the present invention can maintain the initial solubility of the synthesized polypyrrole powder by dropping the oxidizing agent in an aqueous solution in which the pyrrole monomer and the dopant are dissolved, and washing the polymerized solution at low temperature and then filtration under reduced pressure. As a result, the storage performance is further improved, and thus there is a very useful effect of further expanding the application of polypyrrole.
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| US5514771A (en) * | 1994-01-19 | 1996-05-07 | Toho Rayon Co., Ltd. | Process for preparation of soluble ion-doped poly (alkyl-substituted pyrrole) |
| KR960029367A (en) * | 1995-01-19 | 1996-08-17 | 김은영 | Manufacturing method of soluble electrically conductive polypyrrole |
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| US5514771A (en) * | 1994-01-19 | 1996-05-07 | Toho Rayon Co., Ltd. | Process for preparation of soluble ion-doped poly (alkyl-substituted pyrrole) |
| KR960029367A (en) * | 1995-01-19 | 1996-08-17 | 김은영 | Manufacturing method of soluble electrically conductive polypyrrole |
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