KR20030082059A - Novel process of polyaniline - Google Patents
Novel process of polyaniline Download PDFInfo
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- KR20030082059A KR20030082059A KR1020020020587A KR20020020587A KR20030082059A KR 20030082059 A KR20030082059 A KR 20030082059A KR 1020020020587 A KR1020020020587 A KR 1020020020587A KR 20020020587 A KR20020020587 A KR 20020020587A KR 20030082059 A KR20030082059 A KR 20030082059A
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Abstract
Description
본 발명은 폴리아닐린의 새로운 제조 방법에 관한 것이다.The present invention relates to a new process for producing polyaniline.
일반적으로 아닐린과 같은 헤테로 원자를 포함하는 복소환 또는 방향족 화합물을 중합시켜 얻어지는 중합체는 대기 중에서 안정하고 높은 전기전도성을 나타내기 때문에 전도성 재료로서 적합하여 이들에 대한 많은 연구가 이루어지고 있다. 아닐린 중합체는 일반적으로 도핑량의 변화에 따라 전기 전도도 조절이 가능하여 다양한 분야에 응용될 수 있다. 이러한 특성은 범용 플라스틱의 대전방지용이나 전자파차폐용 코팅재료, 도료, 이차전지 및 콘덴서의 전극재료, 반도체 부품, 액정 표시소자 등 다양한 분야에 적용이 가능하다.Generally, polymers obtained by polymerizing heterocycles or aromatic compounds containing heteroatoms such as aniline are suitable as conductive materials because they are stable in air and exhibit high electrical conductivity, and many studies have been made on them. The aniline polymer is generally capable of controlling the electrical conductivity according to the change of the doping amount and thus may be applied to various fields. Such characteristics can be applied to various fields such as antistatic or electromagnetic shielding coating materials for general purpose plastics, coating materials, electrode materials for secondary batteries and capacitors, semiconductor components, and liquid crystal display devices.
전기전도성 고분자(예를 들어, 폴리피롤, 폴리티오펜, 폴리아닐린)는 주쇄를 따라 발달된 π-공액성을 나타내는 구조로서, 이들 화합물들은 그 자체로서는 전도성을 나타내지 않으며, 도판트로 도핑시켰을 때 비로소 전기 전도성을 나타낸다. 전기 전도성 고분자는 전기화학적 중합방법에 의해 필름 형태, 화학적 산화 중합방법에 의해 분말형태의 전기전도성 고분자가 얻어진다. 그러나, 전기화학 중합법으로는 비교적 간단하게 전도성 고분자가 합성될 수 있으나, 필름 형성 면이 전극 표면에 한정되어, 큰 면적의 필름을 얻기가 곤란하며, 제조비용이 높은 문제점이 있다. 또한, 화학산화 중합법으로 얻어진 전도성 고분자는 유기 용매에 대하여 용해하기 어렵기 때문에 캐스팅법으로 필름 형성이 곤란하다.Electroconductive polymers (e.g., polypyrrole, polythiophene, polyaniline) are structures exhibiting π-conjugation developed along the main chain, and these compounds do not exhibit conductivity on their own and are only electrically conductive when doped with dopant. Indicates. The electrically conductive polymer is obtained in the form of a film by an electrochemical polymerization method, or an electrically conductive polymer in the form of a powder by a chemical oxidation polymerization method. However, although the conductive polymer can be synthesized relatively simply by the electrochemical polymerization method, the film forming surface is limited to the electrode surface, so that it is difficult to obtain a large area film, and the manufacturing cost is high. Moreover, since the conductive polymer obtained by the chemical oxidation polymerization method is difficult to dissolve in an organic solvent, film formation is difficult by the casting method.
한편, 폴리아닐린은 화학적 산화에 의하여 비교적 간단히 중합되어지고 높은 전도성을 나타내는 상태에서 공기 중에서도 안정한 특성이 있다. 특히, 산화-환원, 도핑-탈도핑된 상태에서 서로 다른 화학적 구조를 나타낸다. 이들 구조변화는 가역적으로 일어나며, 안정하고 다양한 전기 화학적 특성을 나타내기 때문에 이들의 합성, 구조 연구 및 응용 등에 관한 많은 연구가 진행되어져 오고 있다. 그러나, 다른 전도성 고분자와 같이 폴리아닐린도 π-공액계가 발달된 구조로, 벤젠 고리가 평면 구조로 결합되어 있어 분자쇄가 유연하지 않고, 분자간의 강한 인력이 작용하고, 도판트로 사용된 음이온의 영향 등으로 인하여 유기용매에 불용이며, 가열하여도 용융하지 않는 불융의 성질을 나타내기에, 가공성이 떨어지고, 필름 형성이 되지 않는 큰 결점이 있다. 이와 같은 성질은 폴리아닐린이 여러 가지 다양한 특성과 구조 변화를 나타내는 흥미로운 물질임에도 불구하고, 실제 가공 및 응용 면에서 많은 제약이 되는 요소이다. 이와 같은 단점을 해결하기 위해 폴리아닐린의 화학산화 중합 방법에 관한 많은 연구가 이루어지고 있다.On the other hand, polyaniline has a property of being stable in the air in a state in which it is polymerized relatively simply by chemical oxidation and exhibits high conductivity. In particular, they exhibit different chemical structures in the redox, doped and undoped states. Since these structural changes occur reversibly and exhibit stable and diverse electrochemical properties, many studies on their synthesis, structural studies, and applications have been conducted. However, like other conductive polymers, polyaniline has a π-conjugated structure, and since the benzene ring is bonded in a planar structure, the molecular chain is not flexible, strong attraction between molecules, and the influence of anions used as dopants. Due to this, it is insoluble in an organic solvent and exhibits a property of incompatibility which does not melt even when heated, and thus has a large disadvantage in that workability is poor and film formation is not performed. This property is a limiting factor in practical processing and application, although polyaniline is an interesting material exhibiting a variety of different properties and structural changes. In order to solve such drawbacks, many studies have been made on the chemical oxidation polymerization method of polyaniline.
대한민국 등록특허공보 제 10-0212199호에서는 폴리아닐린 및 폴리피롤을 사용한 복합 수지 제조법을 제시하였다. 이 발명에서는 폴리아닐린 및 폴리피롤과 같은 전도성 고분자를 ABS(acrylonitril-butadiene-styrene) 에멀젼 라텍스 내에서 인-시츄(in-situ)로 중합하여 전도성을 갖는 ABS/폴리아닐린 또는 ABS/폴리피롤 복합 수지 제조법을 제공하였다. 그러나, 이 발명이 제공한 제조방법은 ABS 라텍스 에멀젼에 국한되기 때문에 폴리아닐린의 적용범위에 한계가 있다.Republic of Korea Patent Publication No. 10-0212199 proposed a composite resin manufacturing method using polyaniline and polypyrrole. In the present invention, a conductive polymer such as polyaniline and polypyrrole is polymerized in-situ in an acrylic emulsion latex (acrylonitril-butadiene-styrene) emulsion latex to provide a conductive ABS / polyaniline or ABS / polypyrrole composite resin manufacturing method. . However, the manufacturing method provided by this invention is limited to ABS latex emulsions, which limits the scope of application of polyaniline.
일본 공개특허공보 평06-200017호에서는 황산철을 촉매로 사용한 가용성 폴리아닐린의 제조방법을 제시하였으나, NMP(N-methyl pyrrolidone) 및 DMF(N,N-Dimethyl Formamide)의 가용성만 보고하였다. 수지 코팅제로 일반적으로 사용되는 용매인 톨루엔에는 가용성이 떨어지는 문제점을 가지고 있다.Japanese Laid-Open Patent Publication No. 06-200017 proposed a method for preparing soluble polyaniline using iron sulfate as a catalyst, but reported only solubility of NMP (N-methyl pyrrolidone) and DMF (N, N-dimethyl formamide). Toluene, which is a solvent generally used as a resin coating agent, has a problem of poor solubility.
대한민국 등록특허공보 제 10-0205912호에서는 가용성 폴리아닐린을 제조하기 위하여 제조된 폴리아닐린을 유기용매에 용해시킬 때 도판트를 추가로 첨가시키는 방법을 도입하였다. 이러한 경우, 폴리아닐린의 용해도는 증가하지만, 이 폴리아닐린 용액으로 제조한 필름은 투명도가 저하되고 표면경도가 저하되는 단점을 가지고 있다.Korean Patent Publication No. 10-0205912 has introduced a method in which a dopant is additionally added when the polyaniline prepared to prepare soluble polyaniline is dissolved in an organic solvent. In this case, the solubility of the polyaniline is increased, but the film made with this polyaniline solution has the disadvantage that the transparency is lowered and the surface hardness is lowered.
본 발명은 표면경도와 투명성을 저하시키는 단점을 보완하고 유기용매에 잘 녹는 제품을 만들기 위하여 폴리아닐린의 중합시 메틸 메타크릴레이트 (Methyl methacrylate, MMA), 스틸렌(Styrene) 등과 같은 단량체를 도입함으로써 상기 문제점을 개선한 폴리아닐린의 새로운 제조방법을 제공하고자 한다.The present invention is to solve the above problems by introducing monomers such as methyl methacrylate (MMA), styrene (styrene) during the polymerization of polyaniline to compensate for the disadvantages of lowering the surface hardness and transparency and to make the product soluble in organic solvents To provide a new method for producing a polyaniline improved.
본 발명은 폴리아닐린의 새로운 제조방법을 제공한다. 좀 더 상세하게는 수용액 상태에서 방향족 아민 화합물인 아닐린을 단량체로 사용하고, 도데실벤젠술폰산(Dodecylbenzene sulfonic acid, DBSA)또는 파라톨루엔술폰산(p-Toluenesulfonic acid, PTSA), 폴리스티렌술폰산(Polystyrene sulfonic acid, PSSA)과 같은 유기산 중에 하나 또는 그 이상으로 조합된 조성물을 도판트(dopant)로 사용하고, 유기용매에 대한 가용성을 증가시키기 위하여 메틸 메타크릴레이트(Methyl methacrylate, MMA), 스틸렌(Styrene) 등과 같은 단량체를 첨가하고, 산화제로 암모늄퍼설페이트(APS)를 사용하여 반응시키는 가용성과 투명성이 우수한 폴리아닐린의 제조 방법을 제공한다.The present invention provides a new process for preparing polyaniline. More specifically, an aqueous aromatic amine compound aniline is used as a monomer, and dodecylbenzene sulfonic acid (DBSA) or paratoluenesulfonic acid (p-Toluenesulfonic acid (PTSA), polystyrene sulfonic acid, One or more combinations of organic acids, such as PSSA), are used as dopants, and methyl methacrylate (MMA), styrene, etc., to increase solubility in organic solvents. Provided is a method for producing polyaniline having excellent solubility and transparency by adding a monomer and reacting with ammonium persulfate (APS) as an oxidizing agent.
이하 본 발명의 제조 방법을 좀 더 구체적으로 살펴보면 다음과 같다. 본 발명은 방향족 아민 화합물인 아닐린을 단량체로 하고, 도데실벤젠술폰산 또는 파라톨루엔술폰산, 폴리스티렌술폰산과 같은 유기산 중에 하나 또는 그 이상의 조합을 도판트로 사용하고, 암모늄퍼설페이트를 산화제로 사용하여, 수용액상에서 화학적으로 산화 중합 시켜, 도핑된 상태에서 유기 용매에 용해되는 특성을 갖는 전기전도성 폴리아닐린의 제조방법에 관한 것이다. 여기서, 도데실벤젠술폰산(DBSA)과 같은 유기산은 음이온으로 해리되어 고분자 내에 도핑되어 전도성을 띄게 하는 도판트로 작용하게 된다.Looking in more detail below the manufacturing method of the present invention. The present invention uses an aniline, an aromatic amine compound as a monomer, one or more combinations of dodecylbenzenesulfonic acid or organic acids such as paratoluenesulfonic acid and polystyrenesulfonic acid as a dopant, and an ammonium persulfate as an oxidizing agent. The present invention relates to a method for producing an electroconductive polyaniline chemically oxidatively polymerized and dissolved in an organic solvent in a doped state. Herein, an organic acid such as dodecylbenzenesulfonic acid (DBSA) is dissociated with an anion and is doped into a polymer to act as a dopant that exhibits conductivity.
본 발명의 특징은 폴리아닐린의 용해성을 증가시키기 위하여 가용성 보조제로서 메틸 메타크릴레이트(Methyl methacrylate, MMA), 스틸렌(Styrene) 등과 같은 단량체를 사용하여 아닐린의 중합과 동시에 메틸메타크릴레이트 또는 스틸렌을 고분자로 중합한다. 이 때 첨가된 가용성 보조 단량체의 중합체, 즉 폴리메틸메타크릴레이트 또는 폴리스티렌은 폴리아닐린의 π-공액계가 발달된 구조, 즉 벤젠 고리가 평면 구조로 결합되어 있어 분자쇄가 유연하지 않고, 분자간의 강한 인력이 작용하고 있는 구조를 파괴하여 폴리아닐린의 불용성을 제거하는데 기여를 하고있다.A feature of the present invention is the use of monomers such as methyl methacrylate (MMA), styrene (Styrene), etc. as a soluble adjuvant to increase the solubility of polyaniline at the same time the polymerization of aniline to methyl methacrylate or styrene as a polymer Polymerize. At this time, the polymer of the soluble co-monomer added, that is, polymethyl methacrylate or polystyrene, is a structure in which the π-conjugated system of polyaniline is developed, that is, the benzene ring is bonded in a planar structure, so that the molecular chain is not flexible and strong attraction between molecules It destroys the structure that is working and contributes to eliminating insoluble polyaniline.
본 발명의 제조방법을 상세히 설명하면, 25℃로 온도 조절이 가능한 반응기에, 증류수와 도데실벤젠설폰산 또는 파라톨루엔술폰산, 폴리스티렌술폰산과 같은 유기산 중에 하나 또는 그 이상의 조합으로된 혼합물을 가하고 완전히 용해한다. 이 때, 유기산의 총량은 아닐린 단량체에 대하여 0.6 ~ 1.2 몰비가 바람직하다. 몰비가 0.6 이하에서는 전도성이 떨어지고, 1.2 이상에서는 코팅된 필름의 투명성이 떨어진다.When explaining the production method of the present invention in detail, a mixture of one or more combinations of distilled water and an organic acid such as dodecylbenzenesulfonic acid or paratoluenesulfonic acid, polystyrenesulfonic acid and completely dissolved in a reactor that can be temperature controlled to 25 ℃ do. At this time, the total amount of organic acids is preferably 0.6 to 1.2 molar ratio with respect to the aniline monomer. If the molar ratio is 0.6 or less, the conductivity is poor, and if it is 1.2 or more, the transparency of the coated film is poor.
교반이 완전히 이루어진 후, 단량체로서 방향족 아민 화합물인 아닐린과 용해성을 증가시키기 위한 단량체인 메틸메타크릴레이트 또는 스틸렌을 첨가한 다음, 서서히 교반하면서 단량체들이 완전히 유화된 것을 확인하고, 산화제인 APS 수용액을 서서히 적가하면서 반응시킨다. 이 때 메틸 메타크릴레이트 또는 스틸렌의 첨가량은 아닐린 단량체에 대하여 0.01 ~ 0.3 몰비로 하는 것이 바람직하다. 0.01 몰비 이하에서는 가용성 증가 효과가 없고, 0.3 몰비 이상에서는 전도성을 떨어뜨린다. 여기서 사용된 산화제 APS는 아닐린 단량체에 대하여 0.8 ~1.2 몰비가 바람직하다. 0.8 몰비 이하에서는 전도성이 떨어지고, 1.2 이상에서는 중합도가 높아 가용성이 떨어지는 경향을 나타낸다.After complete stirring, the aromatic amine compound aniline and the monomer methacrylate or styrene to increase the solubility are added, and then the monomers are fully emulsified with gentle agitation. React while adding. At this time, the amount of methyl methacrylate or styrene added is preferably 0.01 to 0.3 molar ratio based on the aniline monomer. If the molar ratio is 0.01 or less, there is no effect of increasing solubility. The oxidizing agent APS used here is preferably 0.8 to 1.2 molar ratio with respect to the aniline monomer. If the molar ratio is 0.8 or less, the conductivity is low, and if it is 1.2 or more, the degree of polymerization is high, so that the solubility tends to be low.
일정 시간 중합 반응을 시킨 후, 과량의 메탄올을 반응액에 첨가하여 반응을 종료시키고 폴리메틸 메타크릴레이트 또는 폴리스틸렌이 포함된 폴리아닐린 복합체의 미세한 분말을 여과하여 얻었다. 얻어진 분말을 과량의 증류수와 메탄올로 충분히 세척하고 여과하여 유기산으로 도핑된 폴리아닐린 복합체를 얻었다. 이렇게얻은 분말을 톨루엔에 용해하면 가용성이 우수한 폴리아닐린 용액을 얻을 수 있었다.After the polymerization reaction was performed for a certain time, excess methanol was added to the reaction solution to terminate the reaction, and fine powder of polyaniline complex containing polymethyl methacrylate or polystyrene was obtained by filtration. The obtained powder was sufficiently washed with excess distilled water and methanol and filtered to obtain a polyaniline complex doped with organic acid. The powder thus obtained was dissolved in toluene to obtain a polyaniline solution having excellent solubility.
전도성 구조를 가진 상태에서 용매에 대해 폴리아닐린이 용해성을 가진다는 것은 전기 전도도를 가진 필름 형성을 가능하게 하고, 어떤 크기나 두께의 필름을 자유자재로 조절할 수 있고, 지금까지 알려진 전기전도성 고분자 필름의 유일한 제조 방법인 전기 화학적 방법보다 대량생산을 가능하게 하고 평활한 표면을 가진 필름 제조가 가능한 장점 등이 있다. 전도성 물질의 표면이 평활하면 할수록 이 물질을 전극재료로 사용하였을 때 전기전자 기능이 균일하여 재현성이 높은 장치를 만들 수 있다. 또한, 접착성이나 강도를 향상시키기 위해 다른 고분자 물질과 용액 블렌딩을 하여 유리판이나 고분자 필름에 코팅시킴으로써 훌륭한 전극재료를 쉽게 제조할 수 있으며, 폴리아닐린 필름의 두께를 조절하면 투명 전극판의 제조도 가능하다.The solubility of polyaniline in solvents in the presence of a conductive structure enables the formation of films with electrical conductivity, freely control films of any size or thickness, and the only known Compared to the electrochemical method, which is a manufacturing method, mass production is possible and a film having a smooth surface can be manufactured. The smoother the surface of the conductive material, the more uniform the electrical and electronic functions can be made when the material is used as an electrode material. In addition, excellent electrode materials can be easily manufactured by coating a glass plate or a polymer film with a solution blended with another polymer material in order to improve adhesiveness or strength, and by controlling the thickness of the polyaniline film, a transparent electrode plate can be manufactured. .
이하 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.
[실시예 1]Example 1
800ml 증류수에 DBSA 65.3 g(0.2 mole)을 녹인 용액을 25℃로 조절 가능한 반응조에 넣고 완전 용해하였다. 단량체인 아닐린 18.6 g(0.2 mole)과 메틸 메타크릴레이트 2.0 g(0.02 mole)을 상기 용액에 넣고 기계적 교반기로 완전히 유화될 때까지 30분간 교반하였다. 교반이 완료되면 산화제인 APS 54.8 g(0.24 mole)을 증류수 200ml에 녹여 약 30분간에 걸쳐 상기 용액에 첨가하여 계속 교반하면서 8시간 동안 반응시킨 후, 200 ㎖의 메탄올을 반응액에 첨가하여 반응을 종료시키고, 얻어진 미세한 폴리아닐린 복합체 분말을 여과하여 얻었다. 여기서 얻어진 분말을 과량의 증류수와 메탄올로 세척하고 여과하여 DBSA가 도핑된 폴리아닐린 복합체를 얻었다. 분말의 폴리아닐린 복합체를 톨루엔에 5% 고형분으로 녹여 폴리아닐린 용액을 제조하였다.A solution in which 65.3 g (0.2 mole) of DBSA was dissolved in 800 ml of distilled water was completely dissolved in a 25 ° C. adjustable reactor. The monomer aniline 18.6 g (0.2 mole) and methyl methacrylate 2.0 g (0.02 mole) was added to the solution and stirred for 30 minutes until fully emulsified with a mechanical stirrer. After the stirring was completed, 54.8 g (0.24 mole) of oxidizing agent was dissolved in 200 ml of distilled water, added to the solution for about 30 minutes, and the reaction was continued for 8 hours while continuing stirring. Then, 200 ml of methanol was added to the reaction solution to react the reaction. It terminated and the obtained fine polyaniline composite powder was obtained by filtration. The powder obtained here was washed with excess distilled water and methanol and filtered to obtain a polyaniline complex doped with DBSA. The polyaniline complex of the powder was dissolved in toluene at 5% solids to prepare a polyaniline solution.
[[ 실시예 2]Example 2
중합방법은 상기 실시예 1과 동일하나 메틸 메타크릴레이트(Methyl methacrylate, MMA) 대신에 스틸렌 단량체 2.1 g(0.02 mole)을 사용하여 중합하여 톨루엔에 용해되어있는 폴리아닐린 용액을 얻었다.The polymerization method was the same as in Example 1, but polymerization was performed using 2.1 g (0.02 mole) of styrene monomer instead of methyl methacrylate (MMA) to obtain a polyaniline solution dissolved in toluene.
[실시예 3]Example 3
800ml 증류수에 파라톨루엔술폰산 38.0 g(0.2 mole)을 녹인 용액을 25℃로 조절 가능한 반응조에 넣고 완전 용해하였다. 아닐린 단량체 18.6 g(0.2 mole)와 메틸 메타크릴레이트 2.0 g(0.02 mole)을 상기 용액에 넣고 기계적 교반기로 완전히 유화될 때까지 30분간 교반하였다. 교반이 완료되면 산화제인 APS 54.8 g(0.24 mole)을 증류수 200ml에 녹여 약 30분간에 걸쳐 상기 용액에 첨가하여 계속 교반하면서 8시간 동안 반응 후, 200 ㎖의 메탄올을 반응액에 첨가하여 반응을 종료시키고, 얻어진 미세한 폴리아닐린 복합체 분말을 여과하여 얻었다. 여기서 얻어진 분말을 과량의 증류수와 메탄올로 세척하고 여과하여 PTSA가 도핑된 폴리아닐린 복합체를 얻었다. 분말의 폴리아닐린 복합체를 톨루엔에 5% 고형분으로 녹여 폴리아닐린 용액을 제조하였다.A solution in which 38.0 g (0.2 mole) of paratoluenesulfonic acid was dissolved in 800 ml distilled water was placed in a reactor at 25 ° C. and completely dissolved. 18.6 g (0.2 mole) of aniline monomer and 2.0 g (0.02 mole) of methyl methacrylate were added to the solution and stirred for 30 minutes until fully emulsified with a mechanical stirrer. After the stirring was completed, 54.8 g (0.24 mole) of oxidizing agent was dissolved in 200 ml of distilled water, and the mixture was added to the solution for about 30 minutes, and the reaction was continued for 8 hours while continuing to stir. The obtained fine polyaniline composite powder was obtained by filtration. The powder obtained here was washed with excess distilled water and methanol and filtered to obtain a polyaniline complex doped with PTSA. The polyaniline complex of the powder was dissolved in toluene at 5% solids to prepare a polyaniline solution.
[[ 실시예 4]Example 4
중합방법은 상기 실시예 3과 동일하나 메틸 메타크릴레이트 대신에 스틸렌 단량체 2.1 g(0.02 mole)을 사용하여 중합하여 톨루엔에 용해되어있는 폴리아닐린 용액을 얻었다.The polymerization method was the same as in Example 3, but polymerized using 2.1 g (0.02 mole) of styrene monomer instead of methyl methacrylate to obtain a polyaniline solution dissolved in toluene.
[실시예 5]Example 5
800ml 증류수에 DBSA 58.8 g(0.18 mole)와 폴리스티렌술폰산 3.7 g(0.02 mole)을 녹인 용액을 25℃로 조절 가능한 반응조에 넣고 완전 용해하였다. 아닐린 단량체 18.6 g(0.2 mole)와 메틸 메타크릴레이트 2.0 g(0.02 mole)을 상기 용액에 넣고 기계적 교반기로 완전히 유화될 때까지 30분간 교반하였다. 교반이 완료되면 산화제인 APS 54.8 g(0.24 mole)을 증류수 200ml에 녹여 약 30분간에 걸쳐 상기 용액에 첨가하여 계속 교반하면서 8시간 동안 반응 후, 200 ㎖의 메탄올을 반응액에 첨가하여 반응을 종료시키고, 얻어진 미세한 폴리아닐린 복합체 분말을 여과하여 얻었다. 여기서 얻어진 분말을 과량의 증류수와 메탄올로 세척하고 여과하여 폴리아닐린복합체를 얻고, 톨루엔에 5% 고형분으로 녹여 폴리아닐린 용액을 제조하였다.A solution obtained by dissolving 58.8 g (0.18 mole) of DBSA and 3.7 g (0.02 mole) of polystyrenesulfonic acid in 800 ml of distilled water was completely dissolved in a reactor controlled at 25 ° C. 18.6 g (0.2 mole) of aniline monomer and 2.0 g (0.02 mole) of methyl methacrylate were added to the solution and stirred for 30 minutes until fully emulsified with a mechanical stirrer. After the stirring was completed, 54.8 g (0.24 mole) of oxidizing agent was dissolved in 200 ml of distilled water, and the mixture was added to the solution for about 30 minutes, and the reaction was continued for 8 hours while continuing to stir. The obtained fine polyaniline composite powder was obtained by filtration. The powder obtained here was washed with excess distilled water and methanol and filtered to obtain a polyaniline complex, which was dissolved in 5% solids in toluene to prepare a polyaniline solution.
[[ 비교예 1]Comparative Example 1
800ml 증류수에 DBSA 65.3 g(0.2 mole)을 녹인 용액을 25℃로 조절 가능한 반응조에 넣고 완전 용해한다. 아닐린 단량체 18.6 g(0.2 mole)를 상기 용액에 넣고 기계적 교반기로 완전히 유화될 때까지 30분간 교반한다. 교반이 완료되면 산화제인 APS 54.8 g(0.22 mole)을 증류수 200ml에 녹여 약 30분간에 걸쳐 상기 용액에 첨가하여 계속 교반하면서 8시간 동안 반응 후, 200 ㎖의 메탄올을 반응액에 첨가하여 반응을 종료시키고, 얻어진 미세한 폴리아닐린 분말을 여과하여 얻었다. 여기서 얻어진 분말을 과량의 증류수와 메탄올로 세척하고 여과하여 폴리아닐린을 얻고, 톨루엔에 5% 고형분으로 녹여 폴리아닐린 용액을 제조하였다.A solution of 65.3 g (0.2 mole) of DBSA dissolved in 800 ml of distilled water is completely dissolved in a 25 ° C. adjustable reactor. 18.6 g (0.2 mole) of aniline monomer are added to the solution and stirred for 30 minutes until fully emulsified with a mechanical stirrer. After the stirring was completed, 54.8 g (0.22 mole) of oxidizing agent was dissolved in 200 ml of distilled water, and the mixture was added to the solution for about 30 minutes, and the reaction was continued for 8 hours while continuing to stir. The fine polyaniline powder thus obtained was obtained by filtration. The powder obtained here was washed with excess distilled water and methanol, filtered to obtain polyaniline, and dissolved in 5% solids in toluene to prepare a polyaniline solution.
[실험예] 물성측정Experimental Example
상기 실시예 1 ~ 5 및 비교예에서 제조한 폴리아닐린 용액 각각에 대해서는 다음과 같은 방법으로 물성을 측정하였다.Physical properties of the polyaniline solutions prepared in Examples 1 to 5 and Comparative Examples were measured by the following methods.
상기 실시예 1 ~ 5 및 비교예에서 얻은 폴리아닐린 용액 각각을 폴리에틸렌테레프탈레이트 필름에 #9 코팅바를 이용하여 얇게 코팅한 후, 건조오븐에서 20초 건조시켰다.Each of the polyaniline solutions obtained in Examples 1 to 5 and Comparative Examples was thinly coated on a polyethylene terephthalate film using a # 9 coating bar, and then dried in a drying oven for 20 seconds.
상기 1)의 필름을 표면저항 측정기(Megaresta Model H0709, ShishidoElectric, Ltd.)를 사용하여 표면저항률을 측정하였다.Surface resistivity of the film of 1) was measured using a surface resistance meter (Megaresta Model H0709, Shishido Electric, Ltd.).
상기 1)의 필름을 육안으로 정면에서 관찰하여 필름의 투명도를 결정하고, 비스듬히 관찰하여 표면 혼탁도를 관찰한 결과를 종합하여 필름 상태를 투명도로 나타내었다.The film of 1) was visually observed from the front to determine the transparency of the film, and the result of observing the surface turbidity was observed at an angle, and the film state was represented as transparency.
결과는 표 1에 나타내었다.The results are shown in Table 1.
◎ (매우양호), ○ (양호), △ (보통), × (나쁨), ×× (매우나쁨)◎ (very good), ○ (good), △ (normal), × (bad), ×× (very bad)
본 발명은 가용성과 투명성이 우수한 폴리아닐린을 제조함으로써, 유기 용매에 쉽게 용해되어 있는 폴리아닐린을 제공하기 때문에 이차 가공성이 뛰어나다.The present invention is excellent in secondary processability because it provides polyaniline that is easily dissolved in an organic solvent by producing polyaniline having excellent solubility and transparency.
본 발명의 폴리아닐린 용액은 범용 플라스틱의 대전방지용이나 전자파 차폐용 코팅재료, 도료, 이차전지 및 콘덴서의 전극재료, 반도체 부품, 액정 표시소자 등 다양한 분야에 적용이 가능하다.The polyaniline solution of the present invention is applicable to various fields such as antistatic or electromagnetic shielding coating materials for general-purpose plastics, paints, electrode materials for secondary batteries and capacitors, semiconductor components, and liquid crystal display devices.
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| KR101053071B1 (en) * | 2010-12-17 | 2011-08-01 | (주)세진에스엠 | Preparation methods of polyanilines with high yields |
| US8279582B2 (en) | 2008-08-05 | 2012-10-02 | Nec Tokin Corporation | Conductive polymer suspension and method for producing the same, conductive polymer material, electrolytic capacitor, and solid electrolytic capacitor and method for producing the same |
| CN104448304A (en) * | 2014-11-24 | 2015-03-25 | 山东科技大学 | Soluble conductive polyaniline nano fiber and preparation method thereof |
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| US5567356A (en) * | 1994-11-07 | 1996-10-22 | Monsanto Company | Emulsion-polymerization process and electrically-conductive polyaniline salts |
| KR100205912B1 (en) * | 1996-07-16 | 1999-07-01 | 이종학 | Process for preparing soluble electrical conductive polyaniline |
| KR100212199B1 (en) * | 1997-08-28 | 1999-08-02 | 박원훈 | Electrical conductive resin and its preparation method |
| JPH11172104A (en) * | 1997-12-15 | 1999-06-29 | Toagosei Co Ltd | Polyaniline derivative |
| KR100490882B1 (en) * | 2001-11-12 | 2005-05-24 | 서광석 | Synthetic Method of Polyaniline and application for electroststic discharge and EMI Shielding |
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2002
- 2002-04-16 KR KR10-2002-0020587A patent/KR100445287B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417676C (en) * | 2004-12-15 | 2008-09-10 | 同济大学 | Method for preparing high-contented polyaniline micro-emulsion |
| US8279582B2 (en) | 2008-08-05 | 2012-10-02 | Nec Tokin Corporation | Conductive polymer suspension and method for producing the same, conductive polymer material, electrolytic capacitor, and solid electrolytic capacitor and method for producing the same |
| KR101053071B1 (en) * | 2010-12-17 | 2011-08-01 | (주)세진에스엠 | Preparation methods of polyanilines with high yields |
| CN104448304A (en) * | 2014-11-24 | 2015-03-25 | 山东科技大学 | Soluble conductive polyaniline nano fiber and preparation method thereof |
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| KR100445287B1 (en) | 2004-08-21 |
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