KR100401349B1 - Fabrication Method of Conductive Polyaniline Spinning Solution - Google Patents
Fabrication Method of Conductive Polyaniline Spinning Solution Download PDFInfo
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- KR100401349B1 KR100401349B1 KR10-2000-0055319A KR20000055319A KR100401349B1 KR 100401349 B1 KR100401349 B1 KR 100401349B1 KR 20000055319 A KR20000055319 A KR 20000055319A KR 100401349 B1 KR100401349 B1 KR 100401349B1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
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Abstract
본 발명은 전도성 고분자 폴리아닐린과 폴리아닐린-브랜드 방사용액의 제조방법에 관한 것으로 더욱 상세하게는 폴리아닐린 염(polyaniline salt)을 사용하여 방사용액을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing conductive polymer polyaniline and polyaniline-brand spinning solution, and more particularly, to a method for preparing a spinning solution using a polyaniline salt.
이를 위하여 본 발명은 폴리아닐린과 폴리아닐린-브랜드 방사용액의 제조에 있어서 기존에 사용하던 폴리아닐린 염기형인 에머날딘 베이스(EB: emeraldine base)를 진한 황산에 용해시키는 방법 대신에 폴리아닐린 염을 진한황산에 용해시키는 방법을 사용하는 것으로 순수한 폴리아닐린 염만을 용해시키거나 폴리아닐린염과 아라미드 또는 나일론 등을 진한 황산에 각각 용해시켜 혼합한 용액을 방사용액으로 사용하는 특징이 있다.To this end, the present invention is a method of dissolving a polyaniline salt in concentrated sulfuric acid instead of dissolving a polyaniline base type emeraldine base (EB) in concentrated sulfuric acid in the preparation of polyaniline and polyaniline-brand spinning solution. It is characterized by using a solution of dissolving only pure polyaniline salt or dissolving polyaniline salt and aramid or nylon in concentrated sulfuric acid, respectively, as a spinning solution.
Description
본 발명은 전도성 고분자 폴리아닐린과 폴리아닐린-브랜드(아라미드, 나일론) 방사용액의 제조 방법에 관한 것으로 더욱 상세하게는 폴리아닐린 염(polyaniline salt)을 사용하여 방사용액을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a conductive polymer polyaniline and a polyaniline-brand (aramid, nylon) spinning solution, and more particularly, to a method for preparing a spinning solution using a polyaniline salt.
일반적으로 폴리아닐린이라고 말하는 시료는 모두 염기형의 시료로 이를 제조하는 방법은 산 수용액하에서 산화제를 가하여 폴리아닐린 염을 제조하고 이를 여과하고, 다시 산 수용액 하에서 처리 후 여과한 후 약염기로 중화하여 염기인 에머날딘 베이스(EB: emeraldine base) 형태로 만들어 진공 건조 후 사용하는 매우 복잡한 제조 공정을 가지고 있다.In general, all of the samples called polyaniline are base-type samples. The method for preparing the polyaniline is a polyaniline salt prepared by adding an oxidizing agent under an aqueous acid solution, filtered, filtered, and then filtered under neutralization with a weak base, followed by neutralization with a weak base. It has a very complicated manufacturing process that is made into the base (EB: emeraldine base) and used after vacuum drying.
진한 황산을 사용하여 폴리아닐린 또는 폴리아닐린-브랜드 섬유를 제조하는 방법은 Polymer Commun. 31,275 (1990) 에 보고된 것으로 98 wt%의 황산 균일 용액으로부터 만들어진 폴리아닐린과 poly(p-phenylene terephthalamide) blend된 섬유로 외부 첨가된 섬유는 순수 폴리아닐린의 전도도는 유지하면서 역학적 성질은 향상시킨 것으로 여기서는 진한 황산용액에 폴리아닐린 염기형을 용해시킨 방법이다. MacDiarmid 등은 U.S. Pat. No. 5,177,187에서 농황산 또는 N-methyl pyrrolidine 에 녹아있는 고분자 용액으로부터 비결정질의 100% 순수 폴리아닐린 섬유의 방사와 제조과정에 대하여 보고하였으나 이 역시 폴리아닐린의 염기형을 용해시킨 방법이다. polyaniline 과 poly(p-phenylene terephthalamide) 의 브랜드 섬유에 대해서는 Jen et al. in U.S. Pat. No. 5,069,820 (melt spinning), Smith et al. in U.S. Pat. No. 5,196,144 (solution spinning from 96% sulfuric acid solutions) and Elsenbaumer in U.S. Pat. No. 5,160,457 (spinning from solutions and doping) 등이 있는데 모든 방법 역시 폴리아닐린의 염기형인 EB를 사용하여 제조한 것이다.A method for producing polyaniline or polyaniline-brand fibers using concentrated sulfuric acid is described in Polymer Commun. 31,275 (1990) reported that the polyaniline and poly (p-phenylene terephthalamide) blended fibers made from 98 wt% sulfuric acid homogeneous solution, which were added externally, improved the mechanical properties while maintaining the conductivity of pure polyaniline. It is a method in which a polyaniline base type is dissolved in a sulfuric acid solution. MacDiarmid et al. U.S. Pat. No. In 5,177,187, the spinning and fabrication of amorphous 100% pure polyaniline fibers from polymer solutions dissolved in concentrated sulfuric acid or N-methyl pyrrolidine are reported. For brand fibers of polyaniline and poly (p-phenylene terephthalamide), see Jen et al. in U.S. Pat. No. 5,069,820 (melt spinning), Smith et al. in U.S. Pat. No. 5,196,144 (solution spinning from 96% sulfuric acid solutions) and Elsenbaumer in U.S. Pat. No. 5,160,457 (spinning from solutions and doping), all of which are also prepared using EB, the base form of polyaniline.
이상에서 열거한 기존의 폴리아닐린 또는 폴리아닐린-브랜드 섬유의 제조방법은 모두 염기형의 폴리아닐린 EB를 사용함으로써 제조 공정이 복잡하고 생산비용이 매우 비싼 단점을 가지고 있었다.The conventional methods for producing polyaniline or polyaniline-brand fibers listed above have disadvantages in that the production process is complicated and the production cost is very expensive by using the basic polyaniline EB.
본 발명은 상기와 같은 문제점을 해소하기 위하여 폴리아닐린의 제조 공정 중 제일 첫단계인 폴리아닐린 염이 합성되는 과정의 생성물을 사용하여 폴리아닐린과 폴리아닐린-브랜드 섬유 제조용 방사용액을 제조하는데 그 목적이 있다.In order to solve the above problems, an object of the present invention is to prepare a spinning solution for preparing polyaniline and polyaniline-brand fibers using a product of a process of synthesizing a polyaniline salt, which is the first step of the polyaniline manufacturing process.
이와같은 목적을 달성하기 위하여 본 발명은, 폴리아닐린 염(염산염, 황산염)을 사용하여 직접 진한 황산 용액에 용해시켜 폴리아닐린 섬유제조용 방사용액을 제조하고 또한 폴리아닐린-브랜드 섬유제조용 방사용액은 폴리아닐린 방사용액에 브랜드 물질을 진한 황산에 녹여 두용액을 혼합하여 제조하는 것에 특징이 있다.In order to achieve the above object, the present invention, by using a polyaniline salt (hydrochloride, sulfate) directly dissolved in a concentrated sulfuric acid solution to prepare a polyaniline fiber manufacturing spinning solution, and polyaniline-brand fiber manufacturing spinning solution is a brand name in the polyaniline spinning solution It is characterized by dissolving the substance in concentrated sulfuric acid to mix the two solutions.
도 1은 기존의 폴리아닐린 방사용액과 폴리아닐린-브랜드 방사용액의 제조 공정과 본 발명의 제조 공정을 비교하여 도시한 것이다.Figure 1 shows a comparison of the production process of the conventional polyaniline spinning solution and polyaniline-brand spinning solution and the manufacturing process of the present invention.
이하 첨부된 도면에 의해 상세히 설명하면 다음과 같다.Hereinafter, described in detail by the accompanying drawings as follows.
도 1은 기존의 폴리아닐린 방사용액과 폴리아닐린-브랜드 방사용액의 제조 공정과 본 발명의 제조 공정을 비교하여 도시한 것이다. 도 1에서 보는 바와 같이 기존의 공정은 매우 복잡한 다단계로 이루어져 있음을 확인할 수 있다. 그러나 본 발병의 공정은 EB 염을 그대로 사용함으로 기존 공정의 처음 3단계를 하나의 공정으로 묶어 단일공정으로 처리함으로 손쉽게 방사용액을 제조 할 수 있다.Figure 1 shows a comparison of the production process of the conventional polyaniline spinning solution and polyaniline-brand spinning solution and the manufacturing process of the present invention. As shown in Figure 1 it can be seen that the existing process consists of a very complex multi-step. However, the process of this disease can be easily prepared by spinning the first three steps of the existing process into a single process by using the EB salt as it is.
일반적으로 폴리아닐린의 합성에 사용되는 산은 염산과 황산으로 합성의 첫단계에서 얻어지는 생성물은 폴리아닐린-염산염, 또는 폴리아닐린-황산염이다. 폴리아닐린-염산염 경우 진한황산과 반응하면 염산염의 형태가 폴리아닐린-황산염의 상태로 변화하여 진한황산에 용해되고, 염화수소 가스가 발생한다. 이는 방사용액 제조시 탈포공정에서 손쉽게 제거 된다. 또한 폴리아닐린-황산염의 경우 손쉽게 진한 황산에 용해되어 방사용액의 제조가 용이하게 된다.Generally, the acid used for the synthesis of polyaniline is hydrochloric acid and sulfuric acid. The product obtained in the first step of the synthesis is polyaniline-hydrochloride, or polyaniline-sulphate. In the case of polyaniline-hydrochloride, when reacted with concentrated sulfuric acid, the form of the hydrochloride changes to the state of polyaniline-sulphate, dissolved in concentrated sulfuric acid, and hydrogen chloride gas is generated. It is easily removed in the defoaming process during spinning solution preparation. In addition, polyaniline sulfate is easily dissolved in concentrated sulfuric acid to facilitate the preparation of the spinning solution.
실시 예1. 폴리아닐린-염산염을 사용한 폴리아닐린 방사용액의 제조Example 1. Preparation of Polyaniline Spinning Solution Using Polyaniline Hydrochloride
40ml(0.22mol)의 정제한 아닐린을 1M 염산 수용액에 넣고 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산 수용액에 넣고 0℃를 유지시켰다. 두용액이 온도 평형에 도달하면 산화제 들어있는 용액을 아닐린이 들어있는 용액에 약 2분간에 걸쳐 서서히 가하고 0℃를 유지시키면서 90분간 교반한다. 이 용액을 여과하여 건조시켜 폴리아닐린-염산염 시료를 얻는다. 폴리아닐린-염산염 15g을 진한황산(98% 이상) 85g에 용해시킨 후 밀폐된 용기에서 염화수소 기체를 탈포 후 방사기에 넣고 질소기체 압력을 가하여 방사하여, 폴리아닐린 섬유를 제조한다.이때 응고욕으로는 증류수를 사용하였고 섬유는 대기 중에서 2일간 건조하였다. 제조된 섬유의 전기전도도는 약10s/cm이었다.40 ml (0.22 mol) of purified aniline was added to 1 M aqueous hydrochloric acid solution and maintained at 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added to 400 ml of 1 M hydrochloric acid aqueous solution and maintained at 0 ° C. When the two solutions reach the temperature equilibrium, the solution containing the oxidant is slowly added to the solution containing aniline over about 2 minutes and stirred for 90 minutes while maintaining 0 ° C. The solution is filtered and dried to obtain a polyaniline hydrochloride sample. After dissolving 15 g of polyaniline hydrochloride in 85 g of concentrated sulfuric acid (98% or more), degassing hydrogen chloride gas in an airtight container in a sealed container and spinning it by applying a nitrogen gas pressure to produce polyaniline fiber. Used and the fibers were dried in air for 2 days. The electrical conductivity of the produced fiber was about 10 s / cm.
실시 예2. 폴리아닐린-황산염을 사용한 폴리아닐린 방사용액의 제조Example 2. Preparation of Polyaniline Spinning Solution Using Polyaniline-Sulfate
40ml(0.22mol)의 정제한 아닐린을 1M 황산 수용액에 넣고 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 황산 수용액에 넣고 0℃를 유지시켰다. 두용액이 온도 평형에 도달하면 산화제 들어있는 용액을 아닐린이 들어있는 용액에 약 2분간에 걸쳐 서서히 가하고 0℃를 유지시키면서 90분간 교반한다. 이 용액을 여과하여 건조시켜 폴리아닐린-황산염 시료를 얻는다. 폴리아닐린-황산염 15g을 진한황산(98% 이상) 85g에 용해시킨 후 방사기에 넣고 질소기체 압력을 가하여 방사하여, 폴리아닐린 섬유를 제조한다.이때 응고욕으로는 증류수를 사용하였고 섬유는 대기 중에서 2일간 건조하였다. 제조된 섬유의 전기전도도는 약 10s/cm이었다.40 ml (0.22 mol) of purified aniline was added to 1 M aqueous sulfuric acid solution to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added to 400 ml of 1 M aqueous sulfuric acid solution to maintain 0 ° C. When the two solutions reach the temperature equilibrium, the solution containing the oxidant is slowly added to the solution containing aniline over about 2 minutes and stirred for 90 minutes while maintaining 0 ° C. The solution is filtered and dried to obtain a polyaniline-sulfate sample. 15 g of polyaniline sulfate was dissolved in 85 g of concentrated sulfuric acid (98% or more), and then spun into a spinning machine and spun under a nitrogen gas pressure to prepare polyaniline fibers. It was. The electrical conductivity of the fibers produced was about 10 s / cm.
실시 예3. 폴리아닐린-염산염을 사용한 폴리아닐린-브랜드 방사용액의 제조Example 3. Preparation of Polyaniline-Brand Spinning Solution Using Polyaniline Hydrochloride
40ml(0.22mol)의 정제한 아닐린을 1M 염산 수용액에 넣고 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 염산 수용액에 넣고 0℃를 유지시켰다. 두용액이 온도 평형에 도달하면 산화제 들어있는 용액을 아닐린이 들어있는 용액에 약 2분간에 걸쳐 서서히 가하고 0℃를 유지시키면서 90분간 교반한다. 이 용액을 여과하여 건조시켜 폴리아닐린-염산염 시료를 얻는다. 폴리아닐린-염산염 15g을 진한황산(98% 이상) 85g에 용해시킨 후 밀폐된 용기에서 염화수소 기체를 탈포한다(용액 A). 아라미드 펄프 15g을 진한황산(98% 이상) 85g에 용해시킨다(용액 B). 용액A와 용액B를 각각 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8,과 1:9로 혼합한 후 각각 방사기에 넣고 질소기체 압력을 가하여 방사하여, 폴리아닐린-아라미드 섬유를 제조한다. 이때 응고욕으로는 증류수를 사용하였고 섬유는 대기 중에서 2일간 건조하였다. 제조된 섬유의 전기전도도는 표 1에 도시한 바와 같다. 5:5까지는 전기전도도의 변화가 거의 없으나 그 이상의 조성에서 아라미드의 조성이 증가하면서 급격히 전기전도도가 감소함을 확인할 수 있다.40 ml (0.22 mol) of purified aniline was added to 1 M aqueous hydrochloric acid solution and maintained at 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added to 400 ml of 1 M hydrochloric acid aqueous solution and maintained at 0 ° C. When the two solutions reach the temperature equilibrium, the solution containing the oxidant is slowly added to the solution containing aniline over about 2 minutes and stirred for 90 minutes while maintaining 0 ° C. The solution is filtered and dried to obtain a polyaniline hydrochloride sample. 15 g of polyaniline-hydrochloride is dissolved in 85 g of concentrated sulfuric acid (98% or more), followed by defoaming hydrogen chloride gas in a closed container (solution A). 15 g of aramid pulp is dissolved in 85 g of concentrated sulfuric acid (98% or more) (solution B). Mix solution A and solution B into 9: 1, 8: 2, 7: 3, 6: 4, 5: 5, 4: 6, 3: 7, 2: 8, and 1: 9, respectively, And spinning by applying nitrogen gas pressure to prepare polyaniline-aramid fibers. At this time, distilled water was used as the coagulation bath, and the fibers were dried in air for 2 days. The electrical conductivity of the fiber produced is as shown in Table 1. There is almost no change in conductivity until 5: 5, but it can be seen that the conductivity decreases rapidly as the composition of the aramid increases.
실시 예4. 폴리아닐린-황산염을 사용한 폴리아닐린-브랜드 방사용액의 제조Example 4. Preparation of Polyaniline-Brand Spinning Solution Using Polyaniline-Sulfate
40ml(0.22mol)의 정제한 아닐린을 1M 황산 수용액에 넣고 0℃를 유지하고 23g의 산화제 (NH4)2S2O8을 400ml의 1M 황산 수용액에 넣고 0℃를 유지시켰다. 두용액이 온도 평형에 도달하면 산화제 들어있는 용액을 아닐린이 들어있는 용액에 약 2분간에 걸쳐 서서히 가하고 0℃를 유지시키면서 90분간 교반한다. 이 용액을 여과하여 건조시켜 폴리아닐린-황산염 시료를 얻는다. 폴리아닐린-황산염 15g을 진한황산(98% 이상) 85g에 용해시킨다(용액 A). 아라미드 펄프 15g을 진한황산(98% 이상) 85g에 용해시킨다(용액 B). 용액A와 용액B를 각각 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8,과 1:9로 혼합한 후 각각 방사기에 넣고 질소기체 압력을 가하여 방사하여, 폴리아닐린-아라미드 섬유를 제조한다.이때 응고욕으로는 증류수를 사용하였고 섬유는 대기중에서 2일간 건조하였다. 제조된 섬유의 전기전도도는 표 1에 도시한 바와 같다. 5:5까지는 전기전도도의 변화가 거의 없으나 그 이상의 조성에서 아라미드의 조성이 증가 하면서 급격히 전기전도도가 감소함을 확인할 수 있다.40 ml (0.22 mol) of purified aniline was added to 1 M aqueous sulfuric acid solution to maintain 0 ° C., and 23 g of oxidizing agent (NH 4 ) 2 S 2 O 8 was added to 400 ml of 1 M aqueous sulfuric acid solution to maintain 0 ° C. When the two solutions reach the temperature equilibrium, the solution containing the oxidant is slowly added to the solution containing aniline over about 2 minutes and stirred for 90 minutes while maintaining 0 ° C. The solution is filtered and dried to obtain a polyaniline-sulfate sample. 15 g of polyaniline sulfate is dissolved in 85 g of concentrated sulfuric acid (98% or more) (solution A). 15 g of aramid pulp is dissolved in 85 g of concentrated sulfuric acid (98% or more) (solution B). Mix solution A and solution B into 9: 1, 8: 2, 7: 3, 6: 4, 5: 5, 4: 6, 3: 7, 2: 8, and 1: 9, respectively, The polyaniline-aramid fiber was prepared by spinning under pressure of nitrogen gas and distilled water was used as a coagulation bath, and the fiber was dried in air for 2 days. The electrical conductivity of the fiber produced is as shown in Table 1. There is almost no change in conductivity until 5: 5, but it can be seen that the conductivity decreases rapidly as the composition of aramid increases.
이상에서 상술한 바와같이 본 발명은 폴리아닐린 염을 사용하여 폴리아닐린 방사용액과 폴리아닐린-브랜드 방사용액을 제조하는 방법에 관한 것으로 폴리아닐린의 합성시 첫단계에 제조되는 폴리아닐린 염을 사용함으로써 제조공정의 단순화, 비용절감 등 많은 장점을 가진 전도성 고분자 섬유의 제조 공정이다. 또한 동일한 공정으로 다양한 전도도를 갖는 전도성 섬유를 제조할 수 있다.As described above, the present invention relates to a method for preparing a polyaniline spinning solution and a polyaniline-brand spinning solution using a polyaniline salt, which simplifies the manufacturing process by using a polyaniline salt prepared in the first step in the synthesis of polyaniline. It is a manufacturing process of conductive polymer fiber with many advantages such as saving. It is also possible to produce conductive fibers having various conductivity in the same process.
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| PCT/KR2001/001568 WO2002024989A1 (en) | 2000-09-20 | 2001-09-19 | Fabrication method of conductive polyaniline spinning solution |
| AU2001292375A AU2001292375A1 (en) | 2000-09-20 | 2001-09-19 | Fabrication method of conductive polyaniline spinning solution |
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| KR101277436B1 (en) | 2010-10-15 | 2013-06-20 | 한국전기안전공사 | Conductive fiber, the method for manufacturing thereof |
| KR101350422B1 (en) | 2012-05-31 | 2014-01-15 | 한양대학교 산학협력단 | Preparation method of conductive polyaniline microfiber using microfluidics, conductive polyaniline microfiber prepared by the same, and microfluidics for preparing conductive polyaniline microfiber |
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| KR100401349B1 (en) * | 2000-09-20 | 2003-10-17 | 스마트텍 주식회사 | Fabrication Method of Conductive Polyaniline Spinning Solution |
| CN105113050A (en) * | 2015-09-06 | 2015-12-02 | 天津工业大学 | Method for preparing conductive polymer/adhesive hybrid fiber through blending spinning |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5788897A (en) * | 1988-08-03 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Electrically conductive fibers |
| WO1999024991A1 (en) * | 1997-11-07 | 1999-05-20 | Corning Communications Limited | Conductive polymer compositions |
| US5911930A (en) * | 1997-08-25 | 1999-06-15 | Monsanto Company | Solvent spinning of fibers containing an intrinsically conductive polymer |
| WO2002024989A1 (en) * | 2000-09-20 | 2002-03-28 | Smart Materials Technology Inc. | Fabrication method of conductive polyaniline spinning solution |
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| US5160457A (en) * | 1987-08-07 | 1992-11-03 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| US5069820A (en) * | 1987-08-07 | 1991-12-03 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| US6001475A (en) * | 1998-10-20 | 1999-12-14 | E. I. Du Pont De Nemours And Company | Silver-containing poly(p-phenylene terephthalamide)/sulfonated polyaniline composite fibers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5788897A (en) * | 1988-08-03 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Electrically conductive fibers |
| US5911930A (en) * | 1997-08-25 | 1999-06-15 | Monsanto Company | Solvent spinning of fibers containing an intrinsically conductive polymer |
| WO1999024991A1 (en) * | 1997-11-07 | 1999-05-20 | Corning Communications Limited | Conductive polymer compositions |
| WO2002024989A1 (en) * | 2000-09-20 | 2002-03-28 | Smart Materials Technology Inc. | Fabrication method of conductive polyaniline spinning solution |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101277436B1 (en) | 2010-10-15 | 2013-06-20 | 한국전기안전공사 | Conductive fiber, the method for manufacturing thereof |
| KR101350422B1 (en) | 2012-05-31 | 2014-01-15 | 한양대학교 산학협력단 | Preparation method of conductive polyaniline microfiber using microfluidics, conductive polyaniline microfiber prepared by the same, and microfluidics for preparing conductive polyaniline microfiber |
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