KR20200077281A - Surface-modified polyketone anion exchange fiber having quaternary ammonium and Method of manufacture thereof - Google Patents
Surface-modified polyketone anion exchange fiber having quaternary ammonium and Method of manufacture thereof Download PDFInfo
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- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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Abstract
Description
본 발명은 4차 암모늄이 도입된 표면개질 폴리케톤 음이온 교환 섬유 및 이의 제조방법에 관한 것이다.The present invention relates to a surface modified polyketone anion exchange fiber into which quaternary ammonium is introduced and a method for manufacturing the same.
최근 산업의 발달로 공장에서 배출되는 유해가스물질에 의한 대기오염이 점차 심각해지고 있다. 이에 따라 유해가스물질을 효과적으로 제거 하기 위한 효율적인 흡착소재의 개발이 요구되고 있다.Recently, with the development of industry, air pollution caused by harmful gas substances discharged from factories has become serious. Accordingly, there is a need to develop an efficient adsorption material for effectively removing harmful gas substances.
유해가스의 흡착 제거기술은 물리적 흡착법과 화학적 흡착법이 있다. 물리적 흡착제로는 활성탄과 제올라이트 등이 있고, 화학적 흡착제로는 이온 교환 수지나 이온 교환 섬유 등이 있다.There are two types of adsorption and removal techniques for harmful gases: physical adsorption and chemical adsorption. Physical adsorbents include activated carbon and zeolite, and chemical adsorbents include ion exchange resins and ion exchange fibers.
물리적 흡착제의 경우 가격이 저렴하고 사용이 간편하나 특정 이온이나 성분에 대한 선택성이 낮다는 단점이 있다. 화학적 흡착제 중 이온 교환 수지는 이온 교환 용량이 크고 가격이 저렴하나 분리공정상 압력손실이 커 공정적용에 한계가 있다는 단점을 가지고 있다.Physical adsorbents are inexpensive and easy to use, but have the disadvantage of low selectivity for specific ions or components. Among chemical adsorbents, ion-exchange resins have the disadvantage of having a large ion-exchange capacity and low price, but a large pressure loss during separation, which limits their application.
반면 화학적 흡착제 중 이온 교환 섬유는 넓은 표면적, 우수한 기계적 강도의 특징을 가지고 있으며, 이온 교환 수지보다 이온 교환 속도가 빨라 대기상의 유해가스 제거에 효과적인 성능을 가지고 있다. On the other hand, among chemical adsorbents, ion-exchange fibers have a characteristic of large surface area and excellent mechanical strength, and have an effective performance in removing harmful gases in the atmosphere due to a faster ion exchange rate than ion-exchange resins.
이러한 이온 교환 섬유의 소재로는 폴리비닐알코올(PVA) 폴리프로필렌(PP), 폴리아크릴로나이트릴(PAN), 등이 사용되고 있다.Polyvinyl alcohol (PVA), polypropylene (PP), polyacrylonitrile (PAN), or the like is used as the material of the ion exchange fiber.
폴리케톤은 비교적 저렴한 일산화탄소와 에틸렌을 모노머로 사용하여 비용 면에서 경쟁력이 있는 소재이며, 내충격성 및 유기용매에 대한 내화학성 또한 우수한 소재이다. 또한 폴리케톤은 카보닐기를 가지고 있어 이를 다양한 관능기로 치환할 수 있고, 이를 이용하여 특정한 화학적 관능기를 폴리케톤에 도입할 수 있다. Polyketone is a material that is competitive in terms of cost by using relatively cheap carbon monoxide and ethylene as monomers, and is also a material having excellent impact resistance and chemical resistance to organic solvents. In addition, the polyketone has a carbonyl group, which can be substituted with various functional groups, and by using this, a specific chemical functional group can be introduced into the polyketone.
이에 착안하여, 특정 이온에 대하여 선택성을 갖는 폴리케톤 이온 교환 섬유 및 이의 제조 방법에 대한 연구에 이르게 되었다.With this in mind, research has been conducted on polyketone ion exchange fibers having selectivity for specific ions and a method for producing the same.
본 발명의 목적은 보다 간단하고 경제적인 폴리케톤 이온 교환 섬유의 제조방법을 제공하는 것이다.An object of the present invention is to provide a simpler and more economical method for producing polyketone ion exchange fibers.
또한 본 발명의 목적은 이온 교환 능력이 우수하고 산성가스의 선택적 제거에 효과적인 폴리케톤 이온 교환 섬유를 제공하는 것이다.It is also an object of the present invention to provide a polyketone ion exchange fiber having excellent ion exchange ability and effective in selective removal of acid gas.
또한 본 발명의 목적은 상술한 이점을 갖는 폴리케톤 이온 교환 섬유를 포함하는 산성가스 제거용 흡착체를 제공하는 것이다.It is also an object of the present invention to provide an adsorbent for removing acidic gas comprising a polyketone ion exchange fiber having the above-described advantages.
상술한 목적을 달성하기 위하여, 본 발명은 폴리케톤 섬유를 2 이상의 아민기를 포함하고 적어도 하나 이상이 1차 아민기인 아민화합물과 반응시켜 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 제조하는 단계 및 상기 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 알킬 할라이드와 반응시켜 4차 암모늄화 표면개질 폴리케톤 섬유를 제조하는 단계를 포함하는 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of preparing a pyrolated surface-modified polyketone fiber in which an amine group is introduced by reacting a polyketone fiber with an amine compound containing at least two amine groups and at least one primary amine group, and A method for producing a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group is introduced, comprising the step of preparing a quaternary ammoniumated surface-modified polyketone fiber by reacting the amine-introduced pyrrolized surface-modified polyketone fiber with an alkyl halide. Gives
또한 본 발명은 상기 제조방법에 의해 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제공한다.In addition, the present invention provides a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group prepared by the above production method is introduced.
또한 본 발명은 4차 암모늄기가 도입된 폴리케톤 음이온 교환 섬유를 포함하는 산성가스 제거용 흡착체를 제공한다.In addition, the present invention provides an adsorbent for removing acidic gas comprising a polyketone anion exchange fiber in which a quaternary ammonium group is introduced.
본 발명에 따르면, 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조할 수 있다. 본 발명의 제조방법은 화학 표면개질을 이용함으로써 기존의 이온 교환 섬유 제조방법인 UV, 플라즈마, 방사선 조사법보다 간단하고 경제적이라는 이점을 갖는다.According to the present invention, surface-modified polyketone anion exchange fibers into which quaternary ammonium groups are introduced can be produced. The manufacturing method of the present invention has the advantage of being simpler and more economical than the conventional method of manufacturing ion-exchange fibers such as UV, plasma, and radiation by using chemical surface modification.
또한 본 발명에 따르면, 상기 제조방법에 의해 제조된 4차 암모늄기가 도입된 표면개질 음이온 교환 섬유를 제공할 수 있다. 이는 이온 교환 능력이 우수하고 산성가스의 선택적 제거에 효과적이다.In addition, according to the present invention, it is possible to provide a surface-modified anion exchange fiber having a quaternary ammonium group introduced by the above production method. It has excellent ion exchange ability and is effective for selective removal of acid gas.
또한 본 발명에 따르면, 상술한 이점을 갖는 4차 암모늄기가 도입된 폴리케톤 음이온 교환 섬유를 포함하는 산성가스 제거용 흡착체를 제공할 수 있다. 이는 다양한 형태로 반도체 클린룸, 공기 정화용 필터, 스크러버 등 다양한 분야에 응용될 수 있다.In addition, according to the present invention, it is possible to provide an adsorbent for removing acidic gas comprising a polyketone anion exchange fiber having a quaternary ammonium group having the above-described advantages. It can be applied to various fields such as semiconductor clean room, air purification filter, and scrubber in various forms.
도 1은 실시예 1의 XPS 분석 결과이다.
도 2는 실시예 1의 SEM 이미지이다.
도 3은 실시예 1 내지 9의 이온 교환 용량을 나타낸 그래프이다.
도 4는 실시예 1,4,7 및 비교예 1의 HCl 흡착 특성 시험 결과 그래프이다.1 is a result of XPS analysis of Example 1.
2 is an SEM image of Example 1.
3 is a graph showing the ion exchange capacity of Examples 1 to 9.
Figure 4 is a graph of the results of the HCl adsorption properties of Examples 1, 4, 7 and Comparative Example 1.
이하에서 본 발명에 대하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail.
본 명세서에서 사용되는 모든 용어(기술 및 과학적 용어를 포함)는 다른 정의가 없다면 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 공통적으로 이해될 수 있는 의미로 사용될 수 있을 것이다. 명세서 전체에서 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다. 또한 단수형은 문구에서 특별히 언급하지 않는 한 복수형도 포함한다.All terms (including technical and scientific terms) used in this specification may be used in a sense that can be commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined. When a part of the specification "includes" a certain component, this means that other components may be further included instead of excluding other components unless specifically stated otherwise. Also, the singular form includes the plural form unless otherwise specified in the phrase.
본 발명에서의 이온 교환 섬유란 그 구조에 이온 교환성 작용기를 가짐으로써 이온 교환 성능을 갖는 섬유를 말한다.The ion exchange fiber in the present invention refers to a fiber having an ion exchange performance by having an ion exchange functional group in its structure.
본 발명은 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법을 제공하는데, 그 제조방법은, 폴리케톤 섬유를 2 이상의 아민기를 포함하고 적어도 하나 이상이 1차 아민기인 아민화합물과 반응시켜 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 제조하는 단계 및 상기 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 알킬 할라이드와 반응시켜 4차 암모늄화 표면개질 폴리케톤 섬유를 제조하는 단계를 포함한다.The present invention provides a method for producing a surface-modified polyketone anion exchange fiber into which a quaternary ammonium group has been introduced, the method of manufacturing, wherein the polyketone fiber contains two or more amine groups and at least one reacts with an amine compound that is a primary amine group. Preparing a pyrolated surface-modified polyketone fiber having an amine group introduced therein and reacting the pyrrolized surface-modified polyketone fiber having an amine group introduced therein with an alkyl halide to produce a quaternary ammoniumated surface-modified polyketone fiber. do.
본 발명의 제조방법은 화학 표면개질을 이용함으로써, 기존의 이온 교환 섬유 제조방법인 UV, 플라즈마, 방사선 조사법보다 간단하고 경제적이라는 이점을 갖는다.The manufacturing method of the present invention has the advantage of being simpler and more economical than the conventional method of manufacturing ion exchange fibers, such as UV, plasma, and radiation, by using chemical surface modification.
본 발명의 일 예에 따를 때, 상기 4차 암모늄화 표면개질 폴리케톤 섬유를 강염기성 용액에 침적시키는 단계를 더 포함할 수 있다. 상기 강염기성 용액은 특별히 제한되는 것은 아니지만 수산화나트륨(NaOH) 또는 수산화칼륨(KOH) 용액일 수 있다. 상기 단계는 보다 구체적으로 상기 4차 암모늄화 표면개질 폴리케톤 섬유를 1.0M의 수산화칼륨 용액에 침적시켜 24시간 진행될 수 있다. 다만 이에 한정되는 것은 아니다. 이러한 단계를 통해 상기 4차 암모늄화 표면개질 폴리케톤 섬유를 강염기인 OH- 폼으로 치환시킴으로써 보다 효과적으로 산성가스를 흡착 제거할 수 있는 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조할 수 있다.According to an example of the present invention, it may further include the step of immersing the quaternary ammoniumated surface-modified polyketone fiber in a strong basic solution. The strong basic solution is not particularly limited, but may be sodium hydroxide (NaOH) or potassium hydroxide (KOH) solution. The step may be more specifically carried out for 24 hours by immersing the quaternary ammonium surface-modified polyketone fiber in a 1.0M potassium hydroxide solution. However, it is not limited thereto. Through these steps, the quaternary ammonium group surface-modified polyketone anion exchange fiber into which the quaternary ammonium group can be adsorbed and removed more effectively can be prepared by substituting the quaternary ammoniumated surface-modified polyketone fiber with a strong base, OH - foam. have.
본 발명의 일 예에 따를 때, 상기 아민화합물은 특별히 제한되는 것은 아니지만, 원활한 폴리케톤의 피롤화 반응 및 적정 수준의 아민기 도입을 위하여 N,N-다이메틸에틸렌다이아민(DME; N,N-Dimethylethylenediamine)을 사용할 수 있다. 용매로는 다이메틸설폭사이드(DMSO; Dimethly sulfoxide)를 사용하여 반응을 진행할 수 있다. 이때 농도는 특별히 제한되는 것은 아니지만 1 내지 30v/v%(DME/DMSO)일 수 있고, 보다 구체적으로는 적정 수준의 아민기 도입을 위해 5 내지 12v/v%일 수 있다. 또한 이때 반응시간은 특별히 제한되는 것은 아니지만, 1 내지 24시간일 수 있고, 보다 구체적으로는 적정 수준의 아민기 도입을 위해 9 내지 15시간일 수 있다. 또한 이때 반응온도는 특별히 제한되는 것은 아니지만 50 내지 100℃일 수 있다. 또한 특별히 제한되는 것은 아니지만 아세트산(acetic acid)을 촉매로 하여 반응을 진행할 수 있다. 하기의 그림은 N,N-다이메틸에틸렌다이아민을 아민화합물로 사용하여 폴리케톤을 피롤화한 반응의 메커니즘이다.According to an example of the present invention, the amine compound is not particularly limited, but for smooth pyrroleation of polyketone and introduction of an appropriate level of amine group, N,N-dimethylethylenediamine (DME; N,N -Dimethylethylenediamine) can be used. Dimethyl sulfoxide (DMSO; Dimethly sulfoxide) can be used as the solvent. At this time, the concentration is not particularly limited, but may be 1 to 30 v/v% (DME/DMSO), and more specifically, 5 to 12 v/v% for introducing an appropriate level of amine group. In addition, the reaction time is not particularly limited, but may be 1 to 24 hours, and more specifically, 9 to 15 hours for introducing an appropriate level of amine groups. In addition, the reaction temperature is not particularly limited, but may be 50 to 100°C. Also, although not particularly limited, the reaction may be performed using acetic acid as a catalyst. The following figure is the mechanism of the reaction of pyrokelation of polyketone using N,N-dimethylethylenediamine as the amine compound.
폴리케톤 섬유의 1,4-다이카보닐과 N,N-다이메틸에틸렌다이아민의 1차 아민기가 아세트 산 촉매 조건 하에 반응하여 피롤화가 이루어진다. 그 반응결과 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유가 제조된다.The primary amine group of 1,4-dicarbonyl and N,N-dimethylethylenediamine of the polyketone fiber is reacted under acetic acid catalyst conditions to make pyrrolylation. As a result of the reaction, a pyrolated surface-modified polyketone fiber into which an amine group has been introduced is produced.
본 발명의 일 예에 따를 때, 상기 알킬 할라이드는 특별히 제한되는 것은 아니지만 메틸 브로마이드(Methyl bromide) 또는 메틸 아이오다이드(Methyl iodide)일 수 있다. 보다 구체적으로 원활한 4차 암모늄화 반응의 진행을 위해 메틸 아이오다이드 일 수 있다. 하기의 그림은 N,N-다이메틸에틸렌다이아민을 아민화합물로 사용하여 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유에 메틸 아이오다이드를 사용하여 4차 암모늄화한 반응의 메커니즘이다.According to an example of the present invention, the alkyl halide is not particularly limited, but may be methyl bromide or methyl iodide. More specifically, it may be methyl iodide for smooth quaternary ammonium reaction. The following figure is the mechanism of the reaction of quaternary ammoniumation using methyl iodide on the pyrolated surface-modified polyketone fiber into which an amine group prepared by using N,N-dimethylethylenediamine as an amine compound is introduced.
피롤에 결합된 아민기와 메틸 아이오다이드가 메틸레이션 반응을 진행하여, 4차 암모늄화 표면개질 폴리케톤 섬유가 제조된다.The amine group bound to the pyrrole and methyl iodide undergo a methylation reaction to produce a quaternary ammoniumated surface-modified polyketone fiber.
본 발명의 일 예에 따를 때, 상기 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 표면의 질소 함량은 특별히 제한되는 것은 아니지만, 탄소, 산소 및 질소 함량 100At% 대비 1 내지 15At%일 수 있다. 보다 구체적으로는, 후속단계를 통해 적정 수준의 이온 교환 성능 및 산성가스 제거 성능을 갖는 4차 암모늄기가 도입된 표면개질 음이온 교환 섬유를 제조하기 위해 8 내지 12At%일 수 있다.According to an example of the present invention, the nitrogen content of the surface of the pyrolated surface-modified polyketone fiber in which the amine group is introduced is not particularly limited, but may be 1 to 15 At% compared to 100 At% of carbon, oxygen and nitrogen. More specifically, it may be 8 to 12At% to prepare a surface-modified anion exchange fiber having a quaternary ammonium group having an appropriate level of ion exchange performance and acid gas removal performance through a subsequent step.
또한 본 발명은 상술한 제조방법에 의하여 제조되는 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제공한다. 본 발명의 음이온 교환 섬유는 그 구조 내에 이온 교환성 작용기로 4차 암모늄기를 가지며, 후술하는 실시예로부터 이온 교환 성능을 갖는 것을 확인할 수 있다. 본 발명에 따른 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 내충격성, 내화학성 및 기계적 강도가 우수한 폴리케톤 섬유를 기반으로 하며, 음이온 교환 성능이 우수한 4차 암모늄기를 가지고 있어 이온 교환 소재로서 다양한 분야에 활용될 수 있다.In addition, the present invention provides a surface-modified polyketone anion exchange fiber into which a quaternary ammonium group prepared by the above-described production method is introduced. It can be confirmed that the anion exchange fiber of the present invention has a quaternary ammonium group as an ion exchangeable functional group in its structure, and has an ion exchange performance from examples described later. The surface-modified polyketone anion exchange fiber in which the quaternary ammonium group according to the present invention is introduced is based on a polyketone fiber having excellent impact resistance, chemical resistance, and mechanical strength, and has an quaternary ammonium group having excellent anion exchange performance, so it is an ion exchange material. As it can be used in various fields.
또한 본 발명은 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 포함하는 산성가스 제거용 흡착체를 제공한다. 본 발명의 흡착체는 상기 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 포함하고 있으면 그 형태는 특별히 제한되지 않으며, 일 예로 실, 직물, 편물, 끈목, 부직포 등의 일반적인 섬유 제품이나 각종 필터 등의 형태를 취할 수 있다. 본 발명의 흡착체는 반도체 클린룸, 공기 정화용 필터, 스크러버 등의 다양한 분야에 응용될 수 있다.In addition, the present invention provides an adsorbent for removing acidic gas comprising a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group is introduced. If the adsorbent of the present invention contains the surface-modified polyketone anion exchange fiber in which the quaternary ammonium group is introduced, its shape is not particularly limited, and for example, general fiber products such as yarns, fabrics, knitted fabrics, braids, non-woven fabrics, etc. It can take the form of a filter or the like. The adsorbent of the present invention can be applied to various fields such as a semiconductor clean room, an air purification filter, and a scrubber.
이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나 하기 실시예는 본 발명의 바람직한 일 실시예일뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.
본 실험에서는 백색의 침상형태인 폴리케톤(Polyketone) 섬유(평균 MW: 200,000, 평균 직경: 0.155mm)를 사용하였다. In this experiment, white needle-like polyketone fibers (average MW: 200,000, average diameter: 0.155 mm) were used.
아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 제조하는 단계는 냉각기, 온도계, 질소 주입구 및 시료주입구가 부착된 100ml 4구 반응기 안에서 진행되었다. 0.56g의 폴리케톤 섬유를 50ml의 다이메틸설폭사이드(DMSO; Dimethyl sulfoxide) 용매에 2.79ml의 N,N-다이메틸에틸렌다이아민(DME; N,N-Dimethylethylenediamine)을 혼합한 5.29v/v% N,N-다이메틸에틸렌다이아민 용액에 침지시켜 반응을 진행하였다. 아세트산(acetic acid) 촉매는 1.44ml 사용하였으며, 70℃의 온도에서 15시간 동안 반응을 진행하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유를 증류수로 여러 번 세척한 후 50℃ 진공오븐에서 24시간 동안 건조시켰다. The step of preparing a pyrolated surface-modified polyketone fiber in which an amine group was introduced was carried out in a 100 ml four-neck reactor equipped with a cooler, thermometer, nitrogen inlet, and sample inlet. 5.29v/v% of 0.56g polyketone fiber mixed with 50ml of dimethylsulfoxide (DMSO; Dimethyl sulfoxide) 2.79ml of N,N-dimethylethylenediamine (DME; N,N-Dimethylethylenediamine) The reaction proceeded by immersion in N,N-dimethylethylenediamine solution. Acetic acid (acetic acid) catalyst was used 1.44ml, the reaction was carried out for 15 hours at a temperature of 70 ℃. The prepared amine group-introduced pyrrolized surface-modified polyketone fiber was washed several times with distilled water and dried in a vacuum oven at 50° C. for 24 hours.
4차 암모늄화 표면개질 폴리케톤 섬유의 제조 단계는 100ml 삼각 플라스크에서 반응을 진행하였다. 상기 건조된 피롤화 표면개질 폴리케톤 섬유를 30ml의 메틸 아이오다이드(Methyl iodide)에 침적시키고 실온에서 48시간 동안 교반시켰다. 4차 암모늄화 표면개질 폴리케톤 섬유를 메탄올과 증류수로 여러 번 세척한 후 50℃ 진공오븐에서 24시간 동안 건조시켜 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. The production step of the quaternary ammonium surface-modified polyketone fiber was carried out in a 100 ml Erlenmeyer flask. The dried pyrolated surface-modified polyketone fiber was immersed in 30 ml of methyl iodide and stirred at room temperature for 48 hours. After washing the quaternary ammoniumated surface-modified polyketone fiber several times with methanol and distilled water, it was dried in a vacuum oven at 50° C. for 24 hours to prepare a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group was introduced.
이 때 반응이 잘 이루어졌는지 확인하기 위하여, X선 광전자 분광법(XPS; X-ray photoelectron spectroscopy) 분석을 수행하였다. Thermo Fisher Scientific사(USA)의 MultiLab 2000를 사용하였고, 0eV에서 1200eV까지의 에너지 분석 범위에서 분석하여 그 결과를 도 1에 기재하였다. 도 1로부터 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 결합에너지(Binding energy) 619eV에서 아이오딘(Iodine)의 3d 피크를, 399eV에서 질소(Nitrogen) 1s peak를 확인할 수 있었다. 다만 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유에서는 질소 1s peak를 확인할 수 있었지만 아이오딘 피크는 확인할 수 없었다. 이러한 결과로부터 4차 암모늄화 반응이 성공적으로 진행되었음을 확인할 수 있다.At this time, in order to confirm whether the reaction was successful, X-ray photoelectron spectroscopy (XPS) analysis was performed. MultiLab 2000 of Thermo Fisher Scientific (USA) was used and analyzed in the energy analysis range from 0 eV to 1200 eV, and the results are shown in FIG. 1. From FIG. 1, the surface modified polyketone anion exchange fiber into which a quaternary ammonium group was introduced was able to confirm a 3d peak of Iodine at 619 eV and a 1 s peak of Nitrogen at 399 eV. However, in the pyrolated surface-modified polyketone fiber in which the amine group was introduced, a 1s peak of nitrogen could be identified, but an iodine peak could not be identified. From these results, it can be confirmed that the quaternary ammoniumation reaction proceeded successfully.
폴리케톤 섬유의 표면 변화를 관찰하기 위해 주사전자현미경(SEM; Scanning Electron Microscopy)을 사용하였다. TESCAN사의 LYRA3 XMU(Czech)를 사용하였으며, 그 결과를 도 2에 기재하였다. 도 2의 (a)는 폴리케톤 섬유, (b)는 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유, (c)는 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 SEM 이미지이다. 도 2에서 보는 바와 표면개질이 진행됨에 따라 폴리케톤 섬유는 그 두께 및 표면 거칠기가 증가하는 경향을 보였다. 이러한 원인은 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 경우 그 표면에 도입된 아민기에 의해 결합구조가 벌크해지기 때문이며, 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 경우 관능기에 의한 분기가 형성되어 그 표면이 불규칙해지기 때문으로 생각된다.Scanning Electron Microscopy (SEM) was used to observe the surface change of polyketone fibers. TESCAN's LYRA3 XMU (Czech) was used, and the results are shown in FIG. 2. Figure 2 (a) is a polyketone fiber, (b) is an SEM image of a pyrolated surface-modified polyketone fiber with an amine group, and (c) a surface-modified polyketone anion exchange fiber with a quaternary ammonium group. As shown in FIG. 2, as the surface modification progressed, the polyketone fibers tended to increase in thickness and surface roughness. This is because in the case of the pyrolated surface-modified polyketone fiber having an amine group introduced, the bonding structure is bulked by an amine group introduced on the surface, and in the case of a surface-modified polyketone anion exchange fiber with a quaternary ammonium group introduced, a functional group It is thought that a branch is formed and the surface becomes irregular.
제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 표면 원소 조성을 확인 하기 위해 SEM-EDS(Energy dispersive spectroscopy) 분석을 하였다. TESCAN사의 LYRA3 XMU(Czech)를 사용하였으며, 그 결과를 표 1에 기재하였다.In order to confirm the surface elemental composition of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber, SEM-EDS (Energy dispersive spectroscopy) analysis was performed. TESCAN's LYRA3 XMU (Czech) was used, and the results are shown in Table 1.
제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 측정을 위하여 건조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 1.0M 수산화칼륨(KOH) 표준용액이 담긴 100ml 삼각플라스크에 넣고 24시간 교반하여 OH- 폼으로 치환시킨 후, 증류수로 여러 번 세척하고 50℃ 진공오븐에 24시간 동안 건조시켰다. 건조시킨 OH- 폼 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 0.1M 염산(HCl) 용액에 넣고 24시간 동안 교반시켜 평형에 도달시킨 다음 페놀프탈레인 2 내지 3 방울 적가 하여 0.1M 수산화나트륨(NaOH) 표준용액으로 적정하였다. 아래 식과 같이 이온 교환 용량(IEC; Ion exchange capacity)을 계산하였고, 그 결과를 도 3에 기재하였다.100 ml containing 1.0 M potassium hydroxide (KOH) standard solution containing the surface modified polyketone anion exchange fiber in which the dried quaternary ammonium group is introduced to measure the ion exchange capacity of the prepared surface modified polyketone anion exchange fiber incorporating the quaternary ammonium group It was placed in an Erlenmeyer flask, stirred for 24 hours, substituted with OH - foam, washed several times with distilled water and dried in a vacuum oven at 50°C for 24 hours. The surface modified polyketone anion exchange fiber into which the dried OH - foam quaternary ammonium group was introduced was placed in a 0.1M hydrochloric acid (HCl) solution, stirred for 24 hours to reach equilibrium, and then added with 2-3 drops of phenolphthalein dropwise to add 0.1M sodium hydroxide ( NaOH) was titrated with a standard solution. Ion exchange capacity (IEC) was calculated as shown in the following equation, and the results are shown in FIG. 3.
여기에서 CHCl은 HCl의 농도(mol/L), VHCl는 HCl의 부피(mL)이며, CNaOH는 NaOH의 농도(mol/L), VNaOH 는 NaOH의 부피(mL)이다. 또한 Wdry는 건조된 섬유의 무게이다. Here, C HCl is the concentration of HCl (mol/L), V HCl is the volume of HCl (mL), C NaOH is the concentration of NaOH (mol/L), and V NaOH is the volume of NaOH (mL). W dry is the weight of the dried fiber.
4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 산성가스 흡착특성을 확인하기 위해 HCl 흡착시험을 수행하였다. HCl 흡착 성능 시험장치는 가스 발생부, 수분 발생부와 흡착칼럼으로 구성하였다. 밸런스 가스로 질소를 사용하였으며, 가스 발생부는 질량 흐름 제어기(MFC; Mass flow controller)를 이용하여 질소 가스와 HCl 가스가 균일하게 혼합 되고 일정농도로 조절될 수 있도록 하였다. 수분 발생부는 증류수를 질소로 버블링하여 습도를 조절할 수 있도록 하였다. 흡착 칼럼부는 내경 6cm, 길이 70cm 인 아크릴 칼럼을 사용하였다. 질량 흐름 제어기를 이용하여 HCl 농도를 300 ppm으로 조절하고 유량은 5 L/min으로 유지시키면서 HCl 가스 흡착시험을 진행하였다. 흡착시험 장치의 평형상태를 유지하기 위하여 30분 동안 공시험(Blank test)를 수행하였다. 유량과 농도가 평형상태에 도달하였을 때 HCl 가스 300ppm을 흡착 칼럼에 통과시키면서 HCl 가스의 파과 시간을 측정하였다. 이때 흡착칼럼 안의 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 5g으로 충진하였다. HCl 가스의 파과시간은 HCl 유출농도가 유입농도의 50%에 해당되는 시점을 기준으로 하였고, HCl 가스의 유입 및 유출농도는 Gastec indicator을 이용하여 검지관의 색깔변화로 유입 및 유출농도를 확인하였다. 흡착 특성 시험의 결과는 도 4에 기재하였다.HCl adsorption test was performed to confirm the acid gas adsorption characteristics of the surface-modified polyketone anion exchange fiber into which the quaternary ammonium group was introduced. The HCl adsorption performance test apparatus consisted of a gas generator, a moisture generator, and an adsorption column. Nitrogen was used as the balance gas, and the gas generating unit was mixed with nitrogen gas and HCl gas by using a mass flow controller (MFC) to be uniformly mixed and controlled at a constant concentration. The moisture generator was made to bubble with distilled water to control the humidity. The adsorption column was used as an acrylic column with an inner diameter of 6 cm and a length of 70 cm. The HCl gas adsorption test was conducted while adjusting the HCl concentration to 300 ppm using a mass flow controller and maintaining the flow rate at 5 L/min. In order to maintain the equilibrium state of the adsorption test apparatus, a blank test was performed for 30 minutes. When the flow rate and concentration reached equilibrium, the breakthrough time of HCl gas was measured while passing 300 ppm of HCl gas through an adsorption column. At this time, the surface modified polyketone anion exchange fiber into which the quaternary ammonium group was introduced in the adsorption column was filled with 5 g. The breakthrough time of HCl gas was based on the time when the HCl outflow concentration was 50% of the inflow concentration, and the inflow and outflow concentrations of the HCl gas were checked by using the Gastec indicator to change the color of the detector tube. . The results of the adsorption properties test are shown in FIG. 4.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계를 12시간 동안 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.A surface-modified polyketone anion exchange fiber in which a quaternary ammonium group was introduced was prepared in the same manner as in Example 1, except that the manufacturing step of the pyrolated surface-modified polyketone fiber in which the amine group was introduced in Example 1 was performed for 12 hours. Did. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계를 9시간 동안 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.A surface-modified polyketone anion exchange fiber in which a quaternary ammonium group was introduced was prepared in the same manner as in Example 1, except that the manufacturing step of the pyrolated surface-modified polyketone fiber in which the amine group was introduced in Example 1 was performed for 9 hours. Did. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민의 양을 3.90ml하여 용액의 농도를 7.24v/v%로, 아세트산 촉매의 양을 2.00ml 하여 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에 기재하였으며, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에, HCl 가스 흡착 성능 시험 결과는 도 4에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was 3.90 ml, so that the concentration of the solution was 7.24 v/v%, and the amount of the acetic acid catalyst was 2.00 ml. The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out, thereby preparing a surface-modified polyketone anion exchange fiber into which a quaternary ammonium group was introduced. The SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber are shown in Table 1, and the ion exchange capacity analysis result of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber is shown in FIG. 3. In the results of the HCl gas adsorption performance test, the results are shown in FIG. 4.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민의 양을 3.90ml하여 용액의 농도를 7.24v/v%로, 아세트산 촉매의 양을 2.00ml 하여 12시간 동안 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was 3.90 ml, so that the concentration of the solution was 7.24 v/v%, and the amount of the acetic acid catalyst was 2.00 ml. Thus, a surface-modified polyketone anion exchange fiber having a quaternary ammonium group introduced therein was prepared in the same manner as in Example 1, except that the reaction was performed for 12 hours. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민의 양을 3.90ml하여 용액의 농도를 7.24v/v%로, 아세트산 촉매의 양을 2.00ml 하여 9시간 동안 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was 3.90 ml, so that the concentration of the solution was 7.24 v/v%, and the amount of the acetic acid catalyst was 2.00 ml. Thus, a surface-modified polyketone anion exchange fiber having a quaternary ammonium group introduced therein was prepared in the same manner as in Example 1, except that the reaction was performed for 9 hours. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민의 양을 5.57ml로 하여 용액의 농도를 10.02v/v%로, 아세트산 촉매의 양을 2.86ml 하여 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에 기재하였으며, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에, HCl 가스 흡착 성능 시험 결과는 도 4에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was set to 5.57 ml, the concentration of the solution was 10.02 v/v%, and the amount of the acetic acid catalyst was 2.86. It was carried out in the same manner as in Example 1, except that the reaction proceeded by ml to prepare a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group was introduced. The SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber are shown in Table 1, and the ion exchange capacity analysis result of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber is shown in FIG. 3. In the results of the HCl gas adsorption performance test, the results are shown in FIG. 4.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민 양을 5.57ml로 하여 용액의 농도를 10.02v/v%로, 아세트산 촉매의 양을 2.86ml 하여 12시간 동안 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was set to 5.57 ml, the concentration of the solution was 10.02 v/v%, and the amount of the acetic acid catalyst was 2.86. It was carried out in the same manner as in Example 1, except that the reaction was performed for 12 hours with ml to prepare a surface modified polyketone anion exchange fiber into which a quaternary ammonium group was introduced. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
실시예 1에서 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 제조단계의 N,N-다이메틸에틸렌다이아민 양을 5.57ml로 하여 용액의 농도를 10.02v/v%로, 아세트산 촉매의 양을 2.86ml 하여 9시간 동안 반응을 진행한 것을 제외하고는 실시예 1과 동일하게 수행하여 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유를 제조하였다. 제조된 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유의 SEM-EDS 분석 값을 표 1에, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 이온 교환 용량 분석 결과를 도 3에 기재하였다.In Example 1, the amount of N,N-dimethylethylenediamine in the step of preparing a pyrolated surface-modified polyketone fiber in which the amine group was introduced was set to 5.57 ml, the concentration of the solution was 10.02 v/v%, and the amount of the acetic acid catalyst was 2.86. It was carried out in the same manner as in Example 1, except that the reaction was performed for 9 hours with ml to prepare a surface-modified polyketone anion exchange fiber into which a quaternary ammonium group was introduced. Table 1 shows the SEM-EDS analysis values of the prepared amine group-introduced pyrrolized surface-modified polyketone fiber in Table 1, and the results of ion exchange capacity analysis of the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber in FIG. 3. Did.
<비교예 1><Comparative Example 1>
실시예 1에서 사용한 폴리케톤 섬유로서, 표면개질을 진행하지 않은 미처리 폴리케톤 섬유이다. SEM-EDS 분석 값을 표 1에, HCl 흡착 성능 시험 결과는 도 4에 기재하였다.The polyketone fiber used in Example 1 is an untreated polyketone fiber that has not undergone surface modification. The SEM-EDS analysis values are shown in Table 1, and the results of the HCl adsorption performance test are shown in FIG. 4.
상기 표 1에서 보는 바와 같이, 폴리케톤 섬유와 반응하는 N,N-다이메틸에틸렌다이아민 용액의 농도와 반응시간이 증가할수록 질소 함량이 8.41At%에서 11.53At%까지 증가하는 것을 확인할 수 있었다.As shown in Table 1, it was confirmed that the nitrogen content increased from 8.41At% to 11.53At% as the concentration and reaction time of the N,N-dimethylethylenediamine solution reacting with the polyketone fiber increased.
이온 교환 용량 분석 결과Ion exchange capacity analysis result
도 3으로부터 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 N,N-다이메틸에틸렌다이아민 용액의 농도와 반응시간이 증가함에 따라 이온 교환 용량이 증가하는 것을 확인할 수 있다. 이는 친수성을 갖는 아민기가 폴리케톤 섬유 기재 내에 도입되면서 이온 교환 용량이 증가하는 것으로 생각된다. 측정된 이온 교환 용량 값은 최대 1.03 meq/g으로 나타났다. 이러한 이온 교환 용량 값을 통해, 제조된 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 이온 교환 섬유로서의 특성을 갖고 있음을 확인할 수 있다. It can be seen from FIG. 3 that the ion-exchange capacity of the surface-modified polyketone anion exchange fiber in which the quaternary ammonium group is introduced increases as the concentration and reaction time of the N,N-dimethylethylenediamine solution increase. It is thought that the ion exchange capacity increases as the amine group having hydrophilicity is introduced into the polyketone fiber substrate. The measured ion exchange capacity value was 1.03 meq/g maximum. Through these ion exchange capacity values, it can be confirmed that the prepared quaternary ammonium group-introduced surface-modified polyketone anion exchange fiber has properties as an ion exchange fiber.
HCl 흡착 특성 시험 결과HCl adsorption properties test results
실시예 1의 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 경우 10분, 실시예 4의 경우 25분, 실시예 7의 경우 40분 동안 100% 흡착 효율을 유지하였다. 흡착 효율이 50%인 시점을 기준으로 할 때, 흡착 파과시간은 실시예 1의 경우 38분, 실시예 4의 경우 55분, 실시예 7의 경우 70분으로, 실시예 7의 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유가 HCl에 대한 흡착효율이 가장 큰 것으로 확인되었다. 이로부터 도입된 아민기 및 4차 암모늄기의 양이 증가할수록 흡착 성능이 향상되는 것을 확인할 수 있었다. 반면 비교예 1의 폴리케톤 섬유는 출구 농도에서 바로 300ppm이 검출되어 흡착 효율이 0%임을 확인하였다. 따라서 본 실험에서 제조한 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 HCl 가스 선택흡착 소재로 적합하다고 생각된다.100% adsorption efficiency was maintained for 10 minutes for the surface-modified polyketone anion exchange fiber in which the quaternary ammonium group of Example 1 was introduced, for 25 minutes for Example 4, and 40 minutes for Example 7. Based on the time point at which the adsorption efficiency is 50%, the adsorption breakthrough time is 38 minutes for Example 1, 55 minutes for Example 4, and 70 minutes for Example 7, and the quaternary ammonium group of Example 7 It was found that the introduced surface-modified polyketone anion exchange fiber had the largest adsorption efficiency for HCl. From this, it was confirmed that the adsorption performance improved as the amount of the introduced amine group and quaternary ammonium group increased. On the other hand, in the polyketone fiber of Comparative Example 1, 300 ppm was detected directly at the outlet concentration, and it was confirmed that the adsorption efficiency was 0%. Therefore, it is considered that the surface-modified polyketone anion exchange fiber in which the quaternary ammonium group prepared in this experiment was introduced is suitable as a material for selective adsorption of HCl gas.
상기와 같은 결과로부터 본 발명의 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 산성가스를 흡착 제거하는 소재로 개발 가능할 것으로 판단된다. 따라서 본 발명의 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유는 다양한 형태의 흡착체에 포함되어 반도체 클린룸, 공기 정화용 필터, 스크러버 등 다양한 분야에서 응용될 수 있을 것으로 생각된다.From the above results, it is determined that the surface modified polyketone anion exchange fiber into which the quaternary ammonium group of the present invention has been introduced can be developed as a material for adsorbing and removing acidic gases. Therefore, it is thought that the surface-modified polyketone anion exchange fiber in which the quaternary ammonium group of the present invention is introduced is included in various types of adsorbents and can be applied in various fields such as a semiconductor clean room, an air purification filter, and a scrubber.
Claims (7)
상기 4차 암모늄화 표면개질 폴리케톤 섬유를 강염기성 용액에 침적시키는 단계를 더 포함하는 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법.According to claim 1,
A method for producing a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group is introduced, further comprising immersing the quaternary ammoniumated surface-modified polyketone fiber in a strong basic solution.
상기 아민화합물은 N,N-다이메틸에틸렌다이아민인 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법.According to claim 1,
The amine compound is N,N- dimethylethylenediamine quaternary ammonium group is introduced surface modification method of the polyketone anion exchange fiber.
상기 알킬 할라이드는 메틸 아이오다이드인 4차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법.According to claim 1,
The alkyl halide is a method for producing a surface-modified polyketone anion exchange fiber in which a quaternary ammonium group which is methyl iodide is introduced.
상기 아민기가 도입된 피롤화 표면개질 폴리케톤 섬유 표면의 질소 함량은 탄소, 산소 및 질소 함량 100At% 대비 1 내지 15At%인 차 암모늄기가 도입된 표면개질 폴리케톤 음이온 교환 섬유의 제조방법.According to claim 1,
The nitrogen content of the surface of the pyrolated surface-modified polyketone fiber in which the amine group is introduced is 1-15At% of the carbon, oxygen, and nitrogen content, and a method for producing a surface-modified polyketone anion exchange fiber in which a primary ammonium group is introduced.
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