KR100840142B1 - Fabrication methods of soluble polypyrrole - Google Patents

Fabrication methods of soluble polypyrrole Download PDF

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KR100840142B1
KR100840142B1 KR1020070038129A KR20070038129A KR100840142B1 KR 100840142 B1 KR100840142 B1 KR 100840142B1 KR 1020070038129 A KR1020070038129 A KR 1020070038129A KR 20070038129 A KR20070038129 A KR 20070038129A KR 100840142 B1 KR100840142 B1 KR 100840142B1
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polypyrrole
dimethylformamide
ethylene glycol
tetrahydrofuran
dichloromethane
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Korean (ko)
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조승구
이성주
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스마트머티리얼스 테크널러지주식회사
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/516—Charge transport ion-conductive

Abstract

A method for preparing a conductive polypyrrole solution is provided to improve the solubility of a polypyrrole in an alcohol or a commercial organic solvent. A method for preparing a conductive polypyrrole solution comprises the steps of dissolving a polypyrrole doped with dimethyl sulfone sulfonic acid(HSS) in a solvent selected from ethylene glycol, methyl pyrrolidone(NMP), methyl sulfoxide(DMSO), dimethylformamide(DMF), tetrahydrofuran(THF), ethylene glycol-methyl pyrrolidone, ethylene glycol-methyl sulfoxide, ethylene glycol-dimethylformamide, dichloromethane-methyl pyrrolidone, dichloromethane-methyl sulfoxide, dichloromethane-dimethylformamide, tetrahydrofuran-methyl sulfoxide, tetrahydrofuran-methyl pyrrolidone and tetrahydrofuran-dimethylformamide.

Description

가용성 폴리피롤의 제조 방법{Fabrication Methods of Soluble Polypyrrole}Fabrication Methods of Soluble Polypyrrole

도 1.은 가용성 폴리피롤의 제조 방법이다. 폴리피롤의 제조 공정에서 피롤 단량체와 디페닐 술폰 술폰산(또는 디페닐 술폰 술폰산염, 즉 리튬염, 나트륨염, 포타슘염, 루비듐염, 세슘염)을 혼합하고 여기에 산화제를 가하여 가용성 폴리 피롤을 제조한다. 제일 처음 단계인 산화과정에서 얻은 폴리피롤을 물로 세척, 건조 후 가용성 폴리피롤 분말을 얻는다.1 is a process for preparing soluble polypyrrole. Soluble polypyrrole is prepared by mixing a pyrrole monomer with diphenyl sulfone sulfonic acid (or diphenyl sulfone sulfonic acid salts, i.e., lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt) in the process of preparing polypyrrole. . The polypyrrole obtained during the first step of oxidation is washed with water and dried to obtain soluble polypyrrole powder.

폴리피롤은 열적안정성과 대기 중에서의 안정성이 좋고 높은 전기전도도를 가지나 일반적인 유기용매에 용해되지 않는 단점이 있어 제한적으로 사용되어 왔다. 유기 용매에 대한 용해도를 높이기 위한 방법으로는 피롤 단량체에 긴 알킬기를 치환하여 폴리피롤을 합성하는 방법이 있으나 치환된 단량체의 가격 등의 문제로 인하여 널리 사용되지는 못하였다. 최근 들어 도데실 벤젠 술폰산(dodecyl benzene sulfonic acid: HDBSA)을 도판트(dopant)로 사용한 폴리피롤이 발명되었으나 메타크레졸(m-cresol)등의 맹독성 용매에 용해되거나 테트라하이드로푸란(THF), 디메틸포름아마이드(DMF), 메틸술폭사이드(DMSO) 등의 용매에 제한적으로 소량 용 해되는 단점이 있다.Polypyrrole has been used in a limited way because it has good thermal stability and stability in the air and has high electrical conductivity but does not dissolve in a general organic solvent. As a method for increasing solubility in an organic solvent, a method of synthesizing polypyrrole by substituting a long alkyl group in a pyrrole monomer has not been widely used due to problems such as the price of a substituted monomer. Recently, polypyrrole using dodecyl benzene sulfonic acid (HDBSA) as a dopant has been invented, but it has been dissolved in highly toxic solvents such as m-cresol, tetrahydrofuran (THF) and dimethylformamide. (DMF), methyl sulfoxide (DMSO) and the like has a disadvantage in that a limited amount of dissolving in a solvent.

미국특허 US2002/0022689 A1 에서는 피롤의 질소 자리를 2개의 메틸기로 치환된 수용성 폴리피롤을 제조하였으나 제조단가가 비싸 상용화에 어려움이 있다.In US Patent US2002 / 0022689 A1, a water-soluble polypyrrole in which the nitrogen site of the pyrrole is substituted with two methyl groups was prepared, but it is difficult to commercialize because of high manufacturing cost.

대한민국특허 10-0318153에서는 나프탈렌술폰산 또는 디이소옥틸술포숙실산 등이 치환된 유기 용매에 가용성인 폴리피롤을 제조하였으나 이들 역시 도판트의 가격이 고가임으로 상용화의 한계를 보인다.In Korean Patent 10-0318153, polypyrrole is soluble in an organic solvent substituted with naphthalenesulfonic acid or diisooctylsulfosuccinic acid, but these also show a limitation of commercialization due to the high price of dopants.

본 발명은 디페닐 술폰 술폰산(Diphenyl Sulfone Sulfonic Acid, C12H10O5S2H, HSS)이 도핑 된 폴리피롤과 디페닐 술폰 술폰산염(Diphenyl Sulfone Sulfonic Acid Salt, C12H10O5S2M, M=알카리금속, 즉 리튬염, 나트륨염, 포타슘염, 루비듐염, 세슘염, MSS)이 도핑된 폴리피롤을 제조하여 알콜이나 상용의 유기 용매에 가용성인 폴리피롤 용액을 제조하고자 한다.The invention diphenylsulfone sulfonate (Diphenyl Sulfone Sulfonic Acid, C 12 H 10 O 5 S 2 H, HSS) is a polypyrrole and diphenyl sulfone sulfonate-doped (Diphenyl Sulfone Sulfonic Acid Salt, C 12 H 10 O 5 S 2 M, M = an alkali metal, that is, a polypyrrole doped with lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, MSS) to prepare a polypyrrole solution soluble in alcohol or a commercial organic solvent.

본 발명은 폴리피롤의 도판트로 디페닐 술폰 술폰산(HSS) 또는 디페닐 술폰 술폰산염, MSS)를 사용하는 것을 특징으로 한다. 이들 도판트들은 용매와의 상호 작용으로 폴리피롤의 용해도를 증가시킨다.The present invention is characterized by using diphenyl sulfone sulfonic acid (HSS) or diphenyl sulfone sulfonate (MSS) as the dopant of polypyrrole. These dopants increase the solubility of polypyrrole in interaction with the solvent.

〈실시 예 1〉<Example 1>

13.2g(0.2mol)의 정제한 피롤 단량체를 디페닐 술폰 술폰산(HSS) 0.1mol이 들어있는 수용액 600ml에 녹여 0℃을 유지하고 22.82g의 산화제 (NH4)2S2O8을 400ml의 수용액에 녹여 0℃을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 피놀 단량체가 포함된 용액에 자석젓개로 저어주며 10분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 24시간정도 교반한다. 반응 시간이 지난 후 침전물을 아스피레이터를 이용하여 뷰흐너 깔대기에 거름 종이를 사용하여 증류수로 여과액이 맑아질 때까지 여과하였다. 약 15분간 더 감압하였다. 70℃ 오븐에서 건조 후 디페닐 술폰 술폰산(HSS)이 도핑된 폴리피롤분말을 얻었다. 0.3g의 분말을 펠렛으로 만들고 전기전도도를 측정한 결과 10S/cm의 전도도를 나타내었다.13.2 g (0.2 mol) of purified pyrrole monomer was dissolved in 600 ml of an aqueous solution containing 0.1 mol of diphenyl sulfone sulfonic acid (HSS) to maintain 0 ° C., and 22.82 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added to 400 ml of aqueous solution. It melt | dissolved in and maintained at 0 degreeC. When the temperature of the two solutions reaches equilibrium, the solution containing the oxidant is stirred in a solution containing the pinol monomer with a magnetic handle and the oxidant is added for 10 minutes. The reaction is stirred for 24 hours while maintaining the reaction temperature. After the reaction time, the precipitate was filtered using an aspirator to remove the filtrate with distilled water using a manure paper in a Buchner funnel. The pressure was further reduced for about 15 minutes. After drying in an oven at 70 ° C., polypyrrole powder doped with diphenyl sulfone sulfonic acid (HSS) was obtained. 0.3g of powder was pelleted and the conductivity measured was 10S / cm.

〈실시 예 2〉<Example 2>

13.2g(0.2mol)의 정제한 피롤 단량체를 디페닐 술폰 술폰리튬염(MSS, 또는 나트륨염, 포타슘염, 루비듐염, 세슘염 ) 0.1mol이 들어있는 수용액 600ml에 녹여 0℃을 유지하고 22.82g의 산화제 (NH4)2S2O8을 400ml의 수용액에 녹여 0℃을 유지하였다. 두 용액의 온도가 평형에 도달하면 산화제가 포함된 용액을 피롤 단량체가 포함된 용액에 자석젓개로 저어주며 10분에 걸쳐 산화제를 넣어준다. 반응물을 반응 온도를 유지하면서 24시간정도 교반한다. 반응 시간이 지난 후 침전물을 아스피레이터를 이용하여 뷰흐너 깔대기에 거름 종이를 사용하여 증류수로 여과액이 맑아질 때까지 여과하였다. 약 15분간 더 감압하였다. 70℃ 오븐에서 건조 후 디페닐 술폰 술폰리튬염(MSS, 또는 나트륨염, 포타슘염, 루비듐염, 세슘염 ) 이 도핑 된 폴리피롤 분말을 얻었다. 0.3g의 분말을 펠렛으로 만들고 전기전도도를 측정한 결과 10S/cm의 전도도를 나타내었다.13.2 g (0.2 mol) of purified pyrrole monomer was dissolved in 600 ml of an aqueous solution containing 0.1 mol of diphenyl sulfone sulfonium salt (MSS, or sodium salt, potassium salt, rubidium salt, cesium salt) and maintained at 0 ° C. The oxidizing agent (NH 4 ) 2 S 2 O 8 was dissolved in 400 ml of aqueous solution and maintained at 0 ° C. When the temperature of the two solutions reaches equilibrium, the solution containing the oxidant is stirred in the solution containing the pyrrole monomer with a magnetic paddle and the oxidant is added for 10 minutes. The reaction is stirred for 24 hours while maintaining the reaction temperature. After the reaction time, the precipitate was filtered using an aspirator to remove the filtrate with distilled water using a manure paper in a Buchner funnel. The pressure was further reduced for about 15 minutes. After drying in an oven at 70 ° C., polypyrrole powder doped with diphenyl sulfone sulfonium salt (MSS, or sodium salt, potassium salt, rubidium salt and cesium salt) was obtained. 0.3g of powder was pelleted and the conductivity measured was 10S / cm.

〈실시 예 3〉<Example 3>

도전성 폴리피롤 용매를 제조하기 위하여 10g의 폴리피롤을 90g의 메틸피롤리디논(NMP) 용매에 용해시켜 제조하였다. 이 용액을 1ml 취하여 필름을 만들고 전기전도도를 측정한 결과 100S/cm의 높은 전기전도도를 나타내었다.To prepare the conductive polypyrrole solvent, 10 g of polypyrrole was prepared by dissolving in 90 g of methylpyrrolidinone (NMP) solvent. 1 ml of this solution was taken to make a film, and the electrical conductivity was measured. The result was a high electrical conductivity of 100 S / cm.

〈실시 예 4〉<Example 4>

도전성 폴리피롤 용매를 제조하기 위하여 10g의 폴리피롤을 90g의 메틸피롤리돈 용매에 용해시켜 제조하였다. 이 용액을 1ml 취하여 필름을 만들고 전기전도도를 측정한 결과 100S/cm의 높은 전기전도도를 나타내었다.To prepare a conductive polypyrrole solvent, 10 g of polypyrrole was prepared by dissolving in 90 g of methylpyrrolidone solvent. 1 ml of this solution was taken to make a film, and the electrical conductivity was measured. The result was a high electrical conductivity of 100 S / cm.

본 발명에 따르면 가용성의 폴리피롤을 제조함으로서 대전방지, 전자기파차폐, 부식방지 등의 기능을 갖는 고분자수지, 고분자필름, 고분자보드 등 정밀 기기 산업에서 요구하는 다양한 제품을 제조 할 수 있다.According to the present invention it is possible to manufacture a variety of products required in the precision equipment industry, such as polymer resin, polymer film, polymer board having functions such as antistatic, electromagnetic wave shielding, corrosion prevention by manufacturing a soluble polypyrrole.

Claims (2)

디페닐 술폰 술폰산(Diphenyl Sulfone Sulfonic Acid, C12H10O5S2H, HSS)이 도핑 된 폴리피롤과 이를 에틸렌글리콜(또는 메틸피롤리디논(NMP), 메틸술폭사이드(DMSO), 디메틸포름아마이드(DMF), 테트라하이드로푸란(THF) 에틸렌글리콜-메틸피롤리디논(NMP), 에틸렌글리콜-메틸술폭사이드(DMSO), 에틸렌글리콜-디메틸포름아마이드(DMF), 디클로로메탄-메틸피롤리디논(NMP), 디클로로메탄-메틸술폭사이드(DMSO), 디클로로메탄-디메틸포름아마이드(DMF), 테트라하이드로푸란-메틸술폭사이드(THF-DMSO), 테트라하이드로푸란-메틸피롤리디논(THF-NMP), 테트라하이드로푸란-디메틸포름아마이드(THF-DMF) )의 용매에 용해시켜 도전성 폴리피롤 용액을 제조하는 방법Polypyrrole doped with Diphenyl Sulfone Sulfonic Acid (C 12 H 10 O 5 S 2 H, HSS) and ethylene glycol (or methylpyrrolidinone (NMP), methylsulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF) ethylene glycol-methylpyrrolidinone (NMP), ethylene glycol-methyl sulfoxide (DMSO), ethylene glycol-dimethylformamide (DMF), dichloromethane-methylpyrrolidinone (NMP ), Dichloromethane-methylsulphoxide (DMSO), dichloromethane-dimethylformamide (DMF), tetrahydrofuran-methylsulphoxide (THF-DMSO), tetrahydrofuran-methylpyrrolidinone (THF-NMP), tetra Method for preparing a conductive polypyrrole solution by dissolving in a solvent of hydrofuran-dimethylformamide (THF-DMF) 디페닐 술폰 술폰산리튬(Lithium Diphenyl Sulfone Sulfonate C12H10O5S2Li)이 도핑 된 폴리피롤, 디페닐 술폰 술폰산나트륨(Sodium Diphenyl Sulfone Sulfonate C12H10O5S2Na)이 도핑 된 폴리피롤 , 디페닐 술폰 술폰산포타슘(Potassium Diphenyl Sulfone Sulfonate C12H10O5S2K)이 도핑 된 폴리피롤, 디페닐 술론 술폰산루비듐(Rubidium Diphenyl Sulfone Sulfonate C12H10O5S2Ru)이 도핑 된 폴리피롤, 디페닐 술폰 술폰산세슘(Cesium Diphenyl Sulfone Sulfonate C12H10O5S2Cs)이 도핑된 폴리피롤 과 이들을 에틸렌글리콜(또는 메틸피롤리디논(NMP), 메틸술폭사이드(DMSO), 디메틸포름아마이드(DMF), 테트라하이드로푸란(THF) 에틸렌글리콜-메틸피롤리디논(NMP), 에틸렌글리콜-메틸술폭사이드(DMSO), 에틸렌글리콜-디메틸포름아마이드(DMF), 디클로로메탄-메틸피롤리디논(NMP), 디클로로메탄-메틸술폭사이드(DMSO), 디클로로메탄-디메틸포름아마이드(DMF), 테트라하이드로푸란-메틸술폭사이드(THF-DMSO), 테트라하이드로푸란-메틸피롤리디논(THF-NMP), 테트라하이드로푸란-디메틸포름아마이드(THF-DMF) )의 용매에 용해시켜 도전성 폴리피롤 용액을 제조하는 방법Polypyrrole doped with Lithium Diphenyl Sulfone Sulfonate C 12 H 10 O 5 S 2 Li, polypyrrole doped with Sodium Diphenyl Sulfone Sulfonate C 12 H 10 O 5 S 2 Na, Polypyrrole doped with Ditasyl Diphenyl Sulfone Sulfonate C 12 H 10 O 5 S 2 K, Polypyrrole doped with Rubidium Diphenyl Sulfone Sulfonate C 12 H 10 O 5 S 2 Ru, Polypyrrole doped with Cesium Diphenyl Sulfone Sulfonate C 12 H 10 O 5 S 2 Cs and ethylene glycol (or methylpyrrolidinone (NMP), methylsulfoxide (DMSO), dimethylformamide (DMF) ), Tetrahydrofuran (THF) ethylene glycol-methylpyrrolidinone (NMP), ethylene glycol-methyl sulfoxide (DMSO), ethylene glycol-dimethylformamide (DMF), dichloromethane-methylpyrrolidinone (NMP), Dichloromethane-methylsulfoxide (DM SO), dichloromethane-dimethylformamide (DMF), tetrahydrofuran-methylsulfoxide (THF-DMSO), tetrahydrofuran-methylpyrrolidinone (THF-NMP), tetrahydrofuran-dimethylformamide (THF- DMF)) to prepare a conductive polypyrrole solution by dissolving in a solvent
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WO2009091184A3 (en) * 2008-01-17 2009-11-05 Lee Sung-Joo Soluble conductive polymer and method for preparing same
KR20200127090A (en) * 2019-04-30 2020-11-10 한국외국어대학교 연구산학협력단 Tracheal tube composition for removal of biofouling

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JPH02215829A (en) * 1987-08-10 1990-08-28 Rockwell Internatl Corp Manufacture of conductive polypyrrole by reacting pyrrole with oxidizing agent/dopant
KR960029367A (en) * 1995-01-19 1996-08-17 김은영 Manufacturing method of soluble electrically conductive polypyrrole
KR0149830B1 (en) * 1995-05-24 1998-10-15 강박광 Process for preparing an aqueous and conductive high molecular compound and its composite
KR20000006968A (en) * 1999-11-16 2000-02-07 장관식 Method for preparation of solubility polypyrrole electrolyte

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Publication number Priority date Publication date Assignee Title
JPH02215829A (en) * 1987-08-10 1990-08-28 Rockwell Internatl Corp Manufacture of conductive polypyrrole by reacting pyrrole with oxidizing agent/dopant
KR960029367A (en) * 1995-01-19 1996-08-17 김은영 Manufacturing method of soluble electrically conductive polypyrrole
KR0149830B1 (en) * 1995-05-24 1998-10-15 강박광 Process for preparing an aqueous and conductive high molecular compound and its composite
KR20000006968A (en) * 1999-11-16 2000-02-07 장관식 Method for preparation of solubility polypyrrole electrolyte

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009091184A3 (en) * 2008-01-17 2009-11-05 Lee Sung-Joo 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
KR20200127090A (en) * 2019-04-30 2020-11-10 한국외국어대학교 연구산학협력단 Tracheal tube composition for removal of biofouling
KR102251462B1 (en) 2019-04-30 2021-05-13 한국외국어대학교 연구산학협력단 Tracheal tube composition for removal of biofouling

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