• Synthesis and Properties of an Ionic Polyacetylene Derivative from the In situ Quaternization Polymerization of 2-Ethynylpyridine Using 1-(Bromoacetyl)pyrene

  • Taehyoung Kim, Sung-Ho Jin*, Jongwook Park**, and Yeong-Soon Gal***,†

  • Advanced Functional Polymers Research Center, Korea Research Institute of Chemical Technology, Daejeon 34114, Korea
    *Department of Chemistry Education, Pusan National University, Busan 46279, Korea
    **Department of Chemical Engineering, Kyunghee University, Suwon 17104, Korea
    ***Department of Fire Safety, Kyungil University, Gyeongsan 38428, Korea

  • 1-(브로모아세틸)피렌을 이용한 2-에티닐피리딘의 4차염화 In-situ 중합을 통한 이온성 폴리아세틸렌 유도체의 합성과 특성

  • 김태형 · 진성호* · 박종욱** · 제갈영순***,†

  • 한국화학연구원 고기능고분자연구센터, *부산대학교 화학교육과, **경희대학교 화학공학과, ***경일대학교 소방방재학과

  • Reproduction, stored in a retrieval system, or transmitted in any form of any part of this publication is permitted only by written permission from the Polymer Society of Korea.


References
  • 1. Gunes, S.; Neugebauer, H.; Sariciftci, N. S. Conjugated Polymer-Based Organic Solar Cells. Chem. Rev. 2007, 107, 1324-1338.
  •  
  • 2. Masuda, T. Substituted Polyacetylenes: Synthesis, Properties, and Functions. Polym. Rev. 2017, 57, 1-24.
  •  
  • 3. Kranthiraja, K.; Kim, H.; Lee, J.; Aryal, U. K.; Reddy, S. S.; Gayathri, R. D.; Gokulnath, T.; Jin, S. H. Side Chain Functionalization of Conjugated Polymer on the Modulation of Photovoltaic Properties of Fullerene and Non-fullerene Organic Solar Cells. Macromol. Res. 2023, 31, 897-905.
  •  
  • 4. Oh, S. H.; Yoo, J.; Lee, J. Comparative Study of Physical Doping and Electrochemical Doping in Polymer Thin-Film Transistors. Macromol. Res. 2023, 31, 1189-1197.
  •  
  • 5. Wang, Z.; Lin, H.; Zhang, M.; Yu, W.; Zhu, C.; Wang, P.; Huang, Y.; Lv, F.; Bai, H.; Wang, S. Water-Soluble Conjugated Polymers for Bioelectronic Systems. Materials Horizons 2023, 10, 1210-1233.
  •  
  • 6. Yao, Z. F.; Wang, J. Y.; Pei, J. Controlling Morphology and Microstructure of Conjugated Polymers via Solution-State Aggregation. Prog. Polym. Sci. 2023, 136, 101626.
  •  
  • 7. Liu, C.; Shao, L.; Chen, S.; Hu, Z.; Huang, F. Recent Progress in π-Conjugated Polymers for Organic Photovoltaics: Solar Cells and Photodectors. Prog. Polym. Sci. 2023, 143, 101711.
  •  
  • 8. Park, J.; Chetan, L.; Kim, H.; Jee, J. S.; Gal, Y. S.; Jin, S. H. New Pyrazine-Based π-Conjugated Polymer for Dopant-free Perovskite Solar Cell. Macromol. Res. 2024, 32, 505-513.
  •  
  • 9. Pak, G. T.; Jo, S.; Lee, T. S. Achieving White Light Emission Using Melamine-Formaldehyde Microcapsules Containing Three Fluorescence Color-Emitting Conjugated Polymers. Macromol. Res. 2024, 32, 597-603.
  •  
  • 10. Freund, M. S.; Deore, B. Self-Doped Conducting Polymers; John Wiley & Sons, Ltd: Chichester, 2007.
  •  
  • 11. Choi, S. K.; Gal, Y. S.; Jin, S. H.; Kim. H. K. Poly(1,6-heptadiyne)-Based Materials by Metathesis Polymerization. Chem. Rev. 2000, 100, 1645-1681.
  •  
  • 12. Gal, Y. S.; Jin, S. H.; Gui, T. L.; Lee, W. C.; Yun, N. G.; Park, S. H.; Lee, S. S.; Bae, J. S. Cyclopolymerization of 2-Ethynyl-N-propargylpyridinium Tetraphenylborate by Transition Metal Catalysts. J. Ind. Eng. Chem. 2005, 11, 432-438.
  •  
  • 13. Okamoto, Y.; Alia, D. Synthesis and Electronic Properties of Polypyridylacetylenes. Chem. Ind. 1964, 29, 1311-1312.
  •  
  • 14. Simionescu, C. I.; Dumitrescu, S.; Percec, V.; Diaconu, I, Polymerization of Acetylene Derivatives. Anion-Radical Salts of TCNQ with Poly(vinyl- and ethynylpyridines). Materiale Plastice 1978, 15, 69-74.
  •  
  • 15. Gal, Y. S.; Cho, H. N.; Kwon, S. K.; Choi, S. K. Polymerization of 2-Ethynylpyridine by Transition Metal Chloride and Organoaluminium Compounds. Polym. Korea 1988, 12, 30-36.
  •  
  • 16. Subramanyam, S.; Blumstein, A. Substituted Extensively Conjugated Ionic Polyacetylenes, US Patent 5,037,916, 1991.
  •  
  • 17. Subramanyam, S.; Blumstein, A. Conjugated Ionic Polyacetylenes. 3. Polymerization of Ethynylpyridinium Salts. Macromolecules 1991, 24, 2668-2674.
  •  
  • 18. Blumstein, A.; Samuelson, L. Highly Conjugated Polyacetylenes: Thin-Film Processing and Potential Applications. Adv. Mater. 1998, 10, 173-176.
  •  
  • 19. Gal, Y. S.; Lee, W. C.; Kim, S. Y.; Park, J. W.; Jin, S. H.; K. N. Koh.; Kim, S. H. Synthesis and Properties of Poly(2-ethynylpyridinium bromide) Having Propargyl Side Chains. J. Polym. Sci.: Part A: Polym. Chem. 2001, 39, 3151-3158.
  •  
  • 20. Kim, T.; Jin, S. H.; Park, J. W.; Lim, K. T.; Kim, S. Y.; Gal, Y. S. Polyacetylene Polyelectrolyte via the Non-catalyst Polymerization of 2-Ethynylpyridine using Heptafluorobenzyl iodide. J. Ind. Eng. Chem. 2020, 87, 130-135.
  •  
  • 21. Kim, T.; Kim, S. Y.; Jin, S. H.; Park, J.; Lim, K. T.; Gal, Y. S. Polyacetylene-Based Polyelectrolyte by the Quaternization Polymerization of 2-Ethynylpyridine using (3-Bromo-1-oxohexyl)ferrocene. Mol. Cryst. Liq. Cryst. 2023, 761, 104-111.
  •  
  • 22. Liu, H.; Kim, D. W.; Blumstein, A.; Kumar, J.; Tripathy, S. K. Nanocomposite Derived from Intercalative Spontaneous Polymerization of 2-Ethynylpyridine within Layered Aluminosilicate: Montmorillonite. Chem. Mater. 2001, 13, 2756-2758.
  •  
  • 23. Faukner, T.; Slany, L.; Sloufova, I.; Vohlidal, J.; Zednik, J. π-Conjugated Polyelectrolytes Derived from 2-Ethynylpyridine: The Effect of Quaternization Agent and Reaction Conditions on the Polymer Structure and SERS Characterization of Nanocomposites with Ag-Nanoparticles. Macromol. Res. 2016, 24, 441-449.
  •  
  • 24. Ko, Y. G.; Kwon, W.; Kim, D. M.; Kim, K.; Gal, Y. S.; Ree, M. Electrically Permanent Characteristics of an Ionic Conjugated Polymer. Polym. Chem. 2012, 3, 2028-2033.
  •  
  • 25. Zhou, C.; Gao, Y.; Chen, D.; Investigation of Pyridine/Propargyl Bromide Reaction and Strong Fluorescence Enhancements of the Resulting Poly(propargylpyridinium bromide). J. Phy. Chem. B 2012, 116, 11552-11559.
  •  
  • 26. Zhang, L.; Lou, X.; Yu, Y.; Qin, J.; Li, Z. A New Disubstituted Polyacetylene Bearing Pyridine Moieties: Convenient Synthesis and Sensitive Chemosensor toward Sulfide Anion with High Selectivity. Macromolecules 2011, 44, 5158-5193.
  •  
  • 27. Nam, S.; Seo, J.; Han, H.; Kim, H.; Hahm, S. K.; Ree, M.; Gal, Y. S.; Anthopoulos, T. D.; Bradley, D. D. C.; Kim, Y. >10% Efficiency Polymer:Fullerene Solar Cells with Polyacetylene-Based Polyelectrolyte Interlayers. Adv. Mater. Interfaces 2016, 3, 1600415.
  •  
  • 28. Aryal, U. K.; Chakravarthi, N.; Park, H. Y.; Bae, H.; Jin, S. H.; Gal, Y. S. Highly Efficient Polyacetylene-Based Polyelectrolytes as Cathode Interfacial Layers for Organic Solar Cell Applications. Org. Elec. 2018, 53, 265-272.
  •  
  • 29. Jia, W. L.; McCormick, T.; Liu, Q. D.; Fukutani, H.; Motala, M.; Wang, R. Y.; Tao, Y.; Wang, S. Diarylamino Functionalized Pyrene Derivatives for Use in Blue OLEDs and Complex Formation. J. Mater. Chem. 2004, 22, 3344-3350.
  •  
  • 30. Figueria-Duarte, T. M.; Mullen, K. Pyrene-Based Materials for Organic Electronics. Chem. Rev. 2011, 111, 7260-7314.
  •  
  • 31. Bachman, J. C.; Kavian, R.; Graham, D. J.; Kim, D. Y.; Noda, S.; Nocera, D. G.; Shao-Horn, Y.; Lee, S. W. Electrochemical Polymerization of Pyrene Derivatives on Functionalized Carbon Nanotubes for Pseudocapacitive Electrodes. Nature Commun. 2015, 6, 7040.
  •  
  • 32. Gong, Y. B.; Zhang, P.; Gu, Y. R.; Wang, J. Q.; Han, M. M.; Chen, C.; Zhan., X. J.; Xie, Z. L.; Zou, B.; Peng, Q.; Chi, Z. G.; Li, Z., The Influence of Molecular Packing on the Emissive Behavior of Pyrene Derivatives: Mechanoluminescence and Mechanochromism. Adv. Opt. Mater. 2018, 6, 1800198.
  •  
  • 33. Gal, Y. S.; Jin, S. H.; Lim, K. T.; Kim, S. H.; Lim, K. T. Synthesis and Electro-optical Properties of Self-doped Ionic Conjugated Polymers: Poly[2-ethynyl-N-(4-sulfobutyl)pyridinium betaine]. Curr. Appl. Phys. 2005, 5, 38-42.
  •  
  • 34. Gal, Y. S.; Jin, S. H.; Park, J.; Lim, K. T. Synthesis and Characterization of a Water-Soluble Ionic Polyacetylene Derivative. Acta Physica Polonica A 2016, 129, 642-646.
  •  
  • 35. Millen, R. P.; de Faria, D. L. A.; Temperini, M. L. A., Vibrational Spectra of 2-Ethynylpyridine and Its Silver Salt. Vibrational Spectroscopy 2001, 27, 89-96.
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2024 Impact Factor : 0.6
  • Indexed in SCIE

This Article

  • 2026; 50(1): 69-75

    Published online Jan 25, 2026

  • 10.7317/pk.2026.50.1.69
  • Received on Jun 13, 2025
  • Revised on Sep 17, 2025
  • Accepted on Sep 23, 2025

Correspondence to

  • Yeong-Soon Gal

  • Department of Fire Safety, Kyungil University, Gyeongsan 38428, Korea

  • E-mail: ysgal@kiu.kr