KR100403380B1 - Fabrication Methods of Spinning Solution for Conductive Polyacrylonitrile (PAN) Fibers - Google Patents
Fabrication Methods of Spinning Solution for Conductive Polyacrylonitrile (PAN) Fibers Download PDFInfo
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- KR100403380B1 KR100403380B1 KR10-2001-0020311A KR20010020311A KR100403380B1 KR 100403380 B1 KR100403380 B1 KR 100403380B1 KR 20010020311 A KR20010020311 A KR 20010020311A KR 100403380 B1 KR100403380 B1 KR 100403380B1
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- Artificial Filaments (AREA)
Abstract
본 발명은 전도성 고분자 sulfonated polyaniline(SPAN)과 polyacrylonitrile (PAN)을 염기를 가한 dimethylsulfoxide(DMSO) 용액에 용해시켜 도전성 아크릴 섬유를 제조하는 방법에 관한 것이다. 이를 위하여 본 발명은 기존의 DMSO용매를 사용한 아크릴 섬유 제조공정에서 방사 용액 제조 시 용매에 염기를 첨가하고 SPAN을 동시에 PAN과 용해시켜 방사용액을 제조함으로써 기존의 공정을 그대로 이용하여 도전성을 띤 아크릴 섬유를 제조할 수 있다.The present invention relates to a method for preparing a conductive acrylic fiber by dissolving a conductive polymer sulfonated polyaniline (SPAN) and a polyacrylonitrile (PAN) in a dimethylsulfoxide (DMSO) solution added with a base. To this end, in the present invention, in the acrylic fiber manufacturing process using a conventional DMSO solvent, by adding a base to the solvent and preparing a spinning solution by dissolving SPAN with PAN at the same time to prepare a spinning solution, the conductive acrylic fiber using the conventional process as it is Can be prepared.
Description
본 발명은 전도성 고분자 sulfonated polyaniline(SPAN)과 polyacrylonitrile (PAN)을 염기를 가한 dimethylsulfoxide(DMSO) 용액에 용해시켜 도전성 아크릴 섬유를 제조하는 방법에 관한 것이다. 기존의 PAN 섬유의 제조 공정 중 DMSO 공정은 DMSO를 용매로 사용하여 방사 용액을 제조하여 섬유를 제조하는 방법이나 이는 PAN 섬유의 단점인 정전기가 매우 잘 발생하는 섬유가 제조된다. 따라서 정전기를 제거하기위한 방법이 많이 연구되고 있으나 아직까지 이를 제거하는 효과적인 방법은 발명되지 않고 있는 실정이다.The present invention relates to a method for preparing a conductive acrylic fiber by dissolving a conductive polymer sulfonated polyaniline (SPAN) and a polyacrylonitrile (PAN) in a dimethylsulfoxide (DMSO) solution added with a base. In the conventional manufacturing process of the PAN fiber, the DMSO process is a method of preparing a fiber by preparing a spinning solution using DMSO as a solvent, but a fiber which generates static electricity, which is a disadvantage of the PAN fiber, is produced very well. Therefore, many methods for removing static electricity have been studied, but the effective method for removing them has not been invented yet.
본 발명의 목적은 정전기를 제거 할 수 있고 더 나아가 매우 높은 전도성을 요구하는 전자기파의 차폐까지 가능한 전도성 고분자가 첨가된 polyacrylonitrile (PAN) 섬유를 가능한 한 기존의 dimethylsulfoxide(DMSO) 공정을 거의 그대로 사용하여 제조할 수 있는 방법을 제공함에 있다.An object of the present invention is to prepare a polyacrylonitrile (PAN) fiber containing a conductive polymer capable of removing static electricity and furthermore shielding electromagnetic waves requiring very high conductivity, using the existing dimethylsulfoxide (DMSO) process as nearly as possible. To provide a way to do it.
도 1은 도전성 PAN 섬유 제조 공정의 개략도1 is a schematic diagram of a conductive PAN fiber manufacturing process
정전기가 발생하는 PAN섬유의 단점을 해결하기 위하여 본 발명에서는 전도성 고분자를 같이 브렌드(blend) 하여 방사 용액을 제조 하였다. 일반적으로 도전성을 띠는 전도성 고분자는 DMSO 용매에 충분한 양이 용해되지 않는다 이러한 단점을 해결하기 위하여 본 발명에서는 DMSO 용매에 염기를 소량 혼합하여 염기성의 유기용매를 제조하고 여기에 전도성 고분자 중에서 염기에 잘 용해되는 SPAN을 용해시켜 도전성 PAN 방사용액을 제조하였다. 이 용액은 SPAN 과 PAN이 혼합 후에도 용액내의 두 물질은 상분리가 일어나지 않는 잘 혼합된 균질 용액임으로 방사 시 단사의 결점이 거의 일어나지 않는 장점을 가지고 있다.In order to solve the disadvantage of the static electricity generated PAN fiber in the present invention by blending the conductive polymer (blend) to prepare a spinning solution. In general, conductive conductive polymers that are conductive do not dissolve in DMSO solvent in sufficient amount. In order to solve this disadvantage, the present invention prepares a basic organic solvent by mixing a small amount of base in DMSO solvent. Dissolved SPAN was dissolved to prepare a conductive PAN spinning solution. This solution has the advantage that even after mixing SPAN and PAN, the two substances in the solution are well mixed homogeneous solutions in which phase separation does not occur.
응고욕으로 염산 용액 등의 산성용액이 순수한 물 보다 훨씬 적합하다. 염기에 용해된 SPAN의 염기형을 산성형으로 바꾸어 용액에 용해되지 않는 형태로 만들어 주고 부가적으로 전기전도도를 1000배 이상 증가시키는 두가지 효과를 동시에 가져온다. 응고욕으로 염산 용액을 사용할 경우 열수 연신 후 건조공정에서 HCl이 가스 형태로 자동적으로 제거되어 세척 공정을 단순화 할 수 있는 장점이 있다.As a coagulation bath, acidic solutions such as hydrochloric acid are much more suitable than pure water. The base type of SPAN dissolved in the base is changed to acidic form, making it insoluble in solution and additionally increasing the electrical conductivity by more than 1000 times. When hydrochloric acid solution is used as a coagulation bath, HCl is automatically removed in the form of gas in the drying process after the hydrothermal stretching, thereby simplifying the cleaning process.
〈실시 예 1〉<Example 1>
DMSO(99%) 용액 83g에 1g의 진한 암모니아수를 가하고 이를 PAN과 SPAN 의 혼합 분말을 16g에 가하여 용해시키고 온도를 약 60℃에서 30분간 방치후 방사기에 넣고 방사 하였다. SPAN은 아닐린 단량체 기준으로 황산화(sulfonation) 비율이 아닐린 단량체(monomer) : SO3H 기 = 1. : 0.25 에서 1: 0.60 의 범위에 황산화가 일어난 것을 사용하였다. 이때 응고욕으로는 0.1 - 1M 염산용액 등 산성용액을 사용하였고 이후의 공정은 기존의 PAN 공정과 동일한 열수연신, 건조, 건열연신 등의 과정을 수행하였다. 단 고강도 산업용사의 건열 열신을 수행할 경우 온도는 150℃이하에서 실행하였다. 전기전도도 측정결과 SPAN의 함량이 10wt% 이상이 함유된 PAN 경우 0.1 S/cm 이상의 전기전도도를 보였고, SPAN의 함량이 증가함에 전기전도도는 증가한다. 가장 높은 전기전도도는 약 100S/cm 이었다. 섬유를 24시간 이상 물에 담가 놓고 다시 건조 후 전기전도도를 측정하여도 10%이하의 전기전도도의 감소가 있었다. 약 10%의 SPAN을 함유한 PAN 섬유의 인장강도 등 기계적 성질은 기존의 PAN 섬유의 물성과 비교하였을 시 90% 이상 거의 비슷한 성질을 나타내었다. SPAN의 양의 증가함에 따라 SPAN이 완전히 용해되지 않을 경우에는 염기를 소량 더 가하면 완전히 용해된다.1 g of concentrated ammonia water was added to 83 g of DMSO (99%) solution, and the mixed powder of PAN and SPAN was added to 16 g to dissolve it, and the temperature was allowed to stand at about 60 ° C. for 30 minutes, followed by spinning. SPAN used aniline monomers having a sulfate ratio in the range of aniline monomers: SO 3 H group = 1.: 0.25 to 1: 0.60 based on aniline monomers. At this time, an acid solution such as 0.1-1 M hydrochloric acid solution was used as a coagulation bath, and the subsequent processes were performed in the same manner as the conventional PAN process, such as hydrothermal stretching, drying, and dry heat stretching. However, the temperature was performed at 150 ° C. or less when performing dry heat hot rolls of high strength industrial companies. As a result of electric conductivity measurement, PAN containing more than 10wt% of SPAN showed more than 0.1 S / cm of electric conductivity. As the content of SPAN increases, the conductivity increases. The highest electrical conductivity was about 100 S / cm. After the fiber was immersed in water for more than 24 hours and dried again, the electrical conductivity was less than 10%. The mechanical properties such as tensile strength of PAN fiber containing about 10% of SPAN showed almost similar properties by more than 90% compared to the properties of conventional PAN fiber. If the SPAN does not dissolve completely as the amount of SPAN increases, a small amount of additional base will dissolve completely.
〈실시 예 2〉<Example 2>
DMSO 용액 83g에 1g의 1M NaOH 수용액을 넣고 이를 PAN과 SPAN 의 혼합 분말을 16g에 가하여 용해시키고 온도를 약 60℃에서 30분간 방치후 방사기에 넣고 방사 하였다. SPAN은 아닐린 단량체 기준으로 황산화(sulfonation) 비율이 아닐린 단량체(monomer) : SO3H 기 = 1. : 0.25 에서 1: 0.60 의 범위에 황산화가 일어난 것을 사용하였다 이때 응고욕으로는 0.1 - 1M 염산용액 등 산성용액을 사용하였고 이후의 공정은 기존의 PAN 공정과 동일한 열수연신, 건조, 건열연신 등의 과정을 수행하였다. 단 건열 열신을 수행할 경우 온도는 150℃이하에서 수행하였다. 전기전도도 측정결과 SPAN의 함량이 10wt% 이상이 함유된 PAN 경우 0.1 S/cm 이상의 전기전도도를 보였고 가장 높은 전기전도도는 약 100S/cm 이었다. 섬유를 24시간 이상 물에 담가 놓고 다시 건조 후 전기전도도를 측정하여도 10%이하의 전기전도도의 감소를 나타내었다.1 g of 1 M NaOH aqueous solution was added to 83 g of DMSO solution, and the mixed powder of PAN and SPAN was added to 16 g to dissolve it, and the temperature was allowed to stand at about 60 ° C. for 30 minutes, followed by spinning. SPAN used aniline monomer (sulfonation ratio) based on the aniline monomer: SO 3 H group = 1.: 0.25 to 1: 0.60 Sulfation occurred in the range of 0.1-1M hydrochloric acid as a coagulation bath An acid solution such as a solution was used, and the subsequent processes performed the same hydrothermal stretching, drying, and dry heat stretching as the conventional PAN processes. When the dry heat thermography is carried out at a temperature below 150 ℃. As a result of electric conductivity measurement, PAN containing more than 10wt% of SPAN showed more than 0.1 S / cm of conductivity and the highest was about 100S / cm. After the fiber was immersed in water for more than 24 hours and dried again, the conductivity was measured to be less than 10%.
〈실시 예 3〉<Example 3>
1%정도의 수분을 함유한 DMSO 용액 84g에 약 10초간 암모니아 기체를 흘려준 후 이를 PAN과 SPAN 의 혼합 분말을 16g에 가하여 용해시키고 온도를 약 60℃에서 30분간 방치후 방사기에 넣고 방사 하였다. SPAN은 아닐린 단량체 기준으로 황산화(sulfonation) 비율이 아닐린 단량체(monomer) : SO3H 기 = 1. : 0.25 에서 1: 0.60 의 범위에 황산화가 일어난 것을 사용하였다. 이때 응고욕으로는 0.1 - 1M 염산용액 등 산성용액을 사용하였고 이후의 공정은 기존의 PAN 공정과 동일한 열수연신, 건조, 건열연신 등의 과정을 수행하였다. 단 고강도 산업용사의 건열 연신을 수행할 경우 온도는 150℃이하에서 실행하였다. 전기전도도 측정결과 SPAN의 함량이 10wt% 이상이 함유된 PAN 경우 0.1 S/cm 이상의 전기전도도를 보였고 가장 높은 전기전도도는 약 100S/cm 이었다. 섬유를 24시간 이상 물에 담가 놓고 다시 건조 후 전기전도도를 측정하여도 10%이하의 전기전도도의 감소를 나타내었다.Ammonia gas was flowed into 84 g of a DMSO solution containing about 1% moisture for about 10 seconds, and the mixed powder of PAN and SPAN was added to 16 g to dissolve it. The temperature was left at about 60 ° C. for 30 minutes, and then spun into a spinning machine. SPAN used aniline monomers having a sulfate ratio in the range of aniline monomers: SO 3 H group = 1.: 0.25 to 1: 0.60 based on aniline monomers. At this time, an acid solution such as 0.1-1 M hydrochloric acid solution was used as a coagulation bath, and the subsequent processes were performed in the same manner as the conventional PAN process, such as hydrothermal stretching, drying, and dry heat stretching. However, when carrying out the dry heat stretching of high-strength industrial company, the temperature was performed at 150 ° C. or lower. As a result of electric conductivity measurement, PAN containing more than 10wt% of SPAN showed more than 0.1 S / cm of conductivity and the highest was about 100S / cm. After the fiber was immersed in water for more than 24 hours and dried again, the conductivity was measured to be less than 10%.
본 발명에 따르면 기존의 PAN 섬유의 DMSO 공정에 용매에 소량의 염기를 가하여 용매로 사용함으로 기존의 공정을 그대로 사용할 수 있고 방사용액 제조 공정 역시 기존의 PAN 방사 용액의 제조와 동일하게 PAN 과 SPAN을 동일한 방법으로 용해시켜 제조한다. 응고욕은 산성용액을 사용하고 용매의 회수는 기존의 DMSO 회수 공정을 그대로 사용할 수 있어 별도의 부가적인 공정없이 기존의 공정을 사용하여 도전성 섬유를 제조함으로 추가적인 부담없이 고부가가치의 도전성 PAN 섬유를 제조할 수 있다.According to the present invention, a small amount of base is added to the DMSO process of a conventional PAN fiber and used as a solvent, so that the existing process can be used as it is. It is prepared by dissolving in the same manner. The coagulation bath uses an acid solution and the solvent recovery can use the existing DMSO recovery process as it is. Therefore, a high value-added conductive PAN fiber can be manufactured without any additional burden by manufacturing the conductive fiber using the existing process without any additional process. can do.
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KR10-2001-0020311A KR100403380B1 (en) | 2001-04-16 | 2001-04-16 | Fabrication Methods of Spinning Solution for Conductive Polyacrylonitrile (PAN) Fibers |
PCT/KR2002/000677 WO2002086205A1 (en) | 2001-04-16 | 2002-04-13 | Fabrication method of conductive polyacrylonitrile spinning solution |
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KR100403381B1 (en) * | 2001-04-19 | 2003-10-30 | 스마트텍 주식회사 | Fabrication Methods of Spinning Solutions for Conductive Polyacrylonitrile (PAN) in NaSCN Solution |
KR100552894B1 (en) * | 2003-09-30 | 2006-02-22 | 스마트머티리얼스 테크널러지주식회사 | Fabrication Methods of Conductive Coating Solution Using NaSCN Aqueous Solution |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS53123453A (en) * | 1977-04-05 | 1978-10-27 | Toray Ind Inc | Acrylic polymer solution having good fiber-forming proterty |
US5135696A (en) * | 1989-10-19 | 1992-08-04 | Ohio State University Research Foundation | Process for forming fibers of sulfonated polyaniline compositions and uses thereof |
KR19990006730A (en) * | 1997-06-04 | 1999-01-25 | 스터링 케미컬즈 인터내셔널, 인코포레이티드 | Antistatic fiber and manufacturing method |
US5911930A (en) * | 1997-08-25 | 1999-06-15 | Monsanto Company | Solvent spinning of fibers containing an intrinsically conductive polymer |
JPH11229232A (en) * | 1998-02-19 | 1999-08-24 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile-based precursor yarn for carbon fiber |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53123453A (en) * | 1977-04-05 | 1978-10-27 | Toray Ind Inc | Acrylic polymer solution having good fiber-forming proterty |
US5135696A (en) * | 1989-10-19 | 1992-08-04 | Ohio State University Research Foundation | Process for forming fibers of sulfonated polyaniline compositions and uses thereof |
KR19990006730A (en) * | 1997-06-04 | 1999-01-25 | 스터링 케미컬즈 인터내셔널, 인코포레이티드 | Antistatic fiber and manufacturing method |
US5911930A (en) * | 1997-08-25 | 1999-06-15 | Monsanto Company | Solvent spinning of fibers containing an intrinsically conductive polymer |
JPH11229232A (en) * | 1998-02-19 | 1999-08-24 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile-based precursor yarn for carbon fiber |
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