Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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An Ionic Polyacetylene Derivative from the Quaternization Polymerization of 2-Ethynylpyridine Using 2-Bromoethyl Isocyanate

2-브로모에틸 이소시아네이트를 이용한 2-에티닐피리딘의 4차염화 중합을 통한 이온성 폴리아세틸렌 유도체

  • Taehyoung Kim (Advanced Function Polymers Research Center, Korea Research Institute of Science and Technology) ;
  • Sung-Ho Jin (Department of Chemistry Education, Pusan National University) ;
  • Jongwook Park (Department of Chemical Engineering, Kyung Hee University) ;
  • Yeong-Soon Gal (Department of Fire Safety, Kyungil University)
  • 김태형 (한국화학연구원 고기능고분자연구센터) ;
  • 진성호 (부산대학교 화학교육학과) ;
  • 박종욱 (경희대학교 화학공학과) ;
  • 제갈영순 (경일대학교 소방방재학과)
  • Received : 2025.06.07
  • Accepted : 2025.07.21
  • Published : 2025.08.10
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Abstract

An ionic polyacetylene derivative with isocyanate group-containing pyridyl substituents was synthesized via the quaternization polymerization of 2-ethynylpyridine using 2-bromoethyl isocyanate. This polymerization has a mechanism by which a monomeric species with an activated acetylene group produced in the first reaction of 2-ethylpyridine using 2-bromoethyl-isocyanate is initiated and propagated without the need for a separate catalyst or initiator. As a result of measuring and analyzing the molecular structure of the obtained polyacetylene using various instrumental methods, it was confirmed that the conjugated backbone system having the designed pyridinium substituents is synthesized. In the UV-visible spectrum of the ionic polyacetylene containing the isocyanate group, the maximum absorption at a longer wavelength was observed at 518 nm, which is attributed to a π→π* transition, and the bandgap was found to be 1.91 eV. The cyclic voltammetry measurement of the polymer showed irreversible electrochemical behavior, with an oxidation peak at 1.00 V and a reduction peak at -1.35 V. Stable results were obtained even after 50 continuous scans. Furthermore, upon increasing the scan rate during the redox process of the polymer, a proportional increase in the oxidation and reduction current values was observed, indicating a normal electrochemical response.

2-브로모에틸 이소시아네이트를 이용한 2-에티닐피리딘의 4차염화 중합을 통하여 새로운 이온성 공액구조 고분자인 이소시아네이트 부분을 갖는 피리디늄 치환기의 폴리아세틸렌 유도체를 합성하였다. 이 중합반응은 2-브로모에틸 이소시아네이트를 이용한 2-에티닐피리딘의 첫 번째 반응에서 생성된 활성화된 아세틸렌 기를 갖는 단량체 종이 별도의 촉매나 개시제의 도움 없이 중합반응이 개시되고 전파되는 메커니즘을 갖는다. 합성한 이온성 폴리아세틸렌 유도체의 분자구조를 여러 가지 분석장비를 이용하여 측정하고 분석한 결과 설계한 치환기를 갖는 공액구조 고분자가 생성되었음을 확인할 수 있었다. 이소시아네이트를 포함하는 폴리아세틸렌 고분자의 UV-visible 스펙트럼에서 장파장의 흡수 최대값은 518 nm이었고 이는 π→π* 전이에 기인한 것으로 밴드갭은 1.91 eV로 나타났다. 고분자의 순환 전압전류 특성 측정결과 1.00 V에서 산화 피크와 -1.35 V에서 환원 피크가 보이는 비가역적인 전기화학적 거동을 보였으며, 50 회까지의 연속 스캔에서도 안정한 결과를 얻을 수 있었다. 또한, 고분자의 산화 환원 과정에 대해 증가하는 스캔 속도변화를 부가하면 산화-환원 전류 값의 증가가 정상적으로 나타남을 확인할 수 있었다.

Keywords

Acknowledgement

This work was supported by the National Research Foundation of Korea (NRF) grant (RS-2023-00243822) of the Ministry of Science and ICT. This work was also supported by the research fund of Kyungil University.

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