| 학회 | 한국고분자학회 |
| 학술대회 | 2004년 가을 (10/08 ~ 10/09, 경북대학교) |
| 권호 | 29권 2호, p.85 |
| 발표분야 | 신규고분자 합성 |
| 제목 | Functional Ionic Conjugated Polymers from Ethynylpyridine and Alkyl Halides |
| 초록 | The polymers having a conjugated backbone are expected to show unique properties such as electrical conductivity, paramagnetism, migration and transfer of energy, color, and chemical reactivity and complex formation ability. Because of these properties, polyacetylene and its homologues have been promising as organic semiconductors, as membranes for gas separation and for liquid-mixture separation, as chiro-optical materials, as side-chain liquid crystals, as materials for chemical sensors, and as materials for nonlinear optical property and for photoluminescence and electroluminescence properties. Pyridine-based acetylenic compounds such as ethynylpyridine, dipyridylacetylene, and dipyridyl-diacetylene are known to be polymerized spontaneously by the simple alkyl halide treatment without giving the N-alkyl product, which is similar to the polymer formation from 4-vinylpyridine including cation radical. The polymerization of ethynylpyridines by using simple alkyl halides such as methyl iodide, 1-octyl bromide, lauryl bromide, etc had been known to proceed even at the mild reaction condition of low temperature (＜50 oC). The activated acetylenic triple bonds of N-alkyl-2-ethynylpyridinium halide was found to be susceptible to the polymerization under mild conditions. Now we report the synthesis of novel ionic conjugated polymers by the direct polymerization of 2-ethynypyridine with functionalized alkyl halides and the characterization of resulting ionic conjugated polymers. Various ionic conjugated polymers were synthesized and characterized. In most cases, the resulting poly(2-ethynypyridinium halide)s having functional groups were completely soluble in water, methanol, DMF, and DMSO. A noble self-dopable conjugated polybetaine, poly[2-ethynyl-N-(4-sulfobutyl)pyridinium betaine] (PESPB) was synthesized by the activated polymerization of 2-ethynylpyridine with 1,4-butanesultone without any additional initiator or catalyst. This polymerization proceeded at the condition of high temperature (130 oC). The polymer yield and inherent viscosity were 82% and 0.13 dL/g, respectively. The chemical structure of PESPB was identified by various instrumental methods to have a conjugated ionic polymer bearing the sulfobetaine moieties. This poly(sulfobetaine) was found to be more soluble in salt solution than in salt-free solution. The photoluminescence peak is located at 530 nm corresponding to the photon energy of 2.34 eV. The photoluminescence intensity was increased as the temperature is increased. At 1 kHz and room temperature, the dielectric constant and electrical conductivity of PESPB were 5.7 and 3.5x10-9 S/cm, respectively. The chemical structure of the resulting polymers was characterized by various instrumental methods such as NMR, IR, UV-visible spectroscopies and elemental analysis to have a conjugated polymer backbone system. We will also discuss the ionic polymerization mechanism The UV-visible and photoluminescence (PL) spectra of the resulting ionic polymers were measured and discussed. The modification of these polymers by the ion-exchange reaction with NaBPh4, NaN3, and NaClO4 was performed, and the structure and properties of the modified ionic polymers were also discussed. 참고문헌 1. S. K. Choi, Y. S. Gal, S. H. Jin, and H. K. Kim, Chem. Rev., 100, 1645 (2000). 2. Y. S. Gal, S. H. Jin, J. W. Park, W. C. Lee, H. S. Lee, and S. Y. Kim, J. Polym. Sci.: Part A: Polym. Chem., 39, 4101 (2001). 3. S. H. Jin, M. S. Jang, H. S. Suh, H. N. Cho, J. H. Lee, and Y. S. Gal, Chem. Mater., 14, 643 (2002). 4. Y. S. Gal, S. H. Jin, and S. K. Choi, J. Mol. Cat. A: Chem., 213, 115 (2004). |
| 저자 | 제갈영순1, 진성호2 |
| 소속 | 1경일대, 2부산대 |
| 키워드 | Polyacetylene; conjugated polymer; photoluminescence; electroluminescence; ion-exchange |
