| 학회 | 한국고분자학회 |
| 학술대회 | 2005년 가을 (10/13 ~ 10/14, 제주 ICC) |
| 권호 | 30권 2호 |
| 발표분야 | 고분자 합성 |
| 제목 | Synthesis and Electro-Optical Properties of Poly(2-ethynylpyridinium bromide) Derivatives with Spiroxazine Moiety |
| 초록 | Polyelectrolytes are charged macromolecules containing a large number of ionizable or ionic groups. The polyelectrolytes include proteins, nucleic acids, pectins, polyacrylic acid, and polystyrene sulfonate. A few example of conjugated polyelectrolytes include poly(propiolic salt)s, triethylammonium salt of poly(6-bromo-1-hexyne), and poly(ethynylpyridine)s. In 1990, Blumstein et al prepared the well-defined ionic polyacetylenes through the activated polymerization of ethynylpyridines with alkyl halides. Due to their extensive conjugation and ionic nature, these ionic polyacetylenes have potentials as materials for mixed ionic and electronic conductivity, energy storage devices such as batteries, permselective membrane, light-emitting devices. Recently, photochromic materials have gained much attention, and they now constitute an active research area because of their tremendous importance in biological phenomena and in their potential applications in the areas of linear and nonlinear optics. Although spiroheterocyclic compounds have attracted significant attention because of their potential use, they still await major commercial exploitation. One of the prime reasons for the lack of industrial applications for photo- and thermochromic materials, particularly organic compounds, is their poor durability. Although the thermo- and photochromism of spiropyran has been extensively studied, only little work has been carried out on spironaphthoxazine dyes. These two classes of compounds are similar in many respects, but the replacement of benzopyran ring by a naphthoxazine ring, which results in spironaphthoxazine, greatly improves resistance to prolonged UV irradiation, which confers greatly commercial importance. Here, we report the synthesis of new ionic conjugated polymer, poly[2-ethynyl-N-hexyloxyspiroxazine pyridinium bromide] by the activated polymerization of 2-ethynylpyridine with 1,3,3-trimethyl-6’-bromohexyloxyspiro[2H]-indol-2,3’-[3H]-naphth[2,1-b][1,4]oxazine, and the electro-optical properties of the resulting polymer. A noble conjugated ionic polymer with photochromic spiroxazine moiety, poly[2-ethynyl-N-hexyloxyspiroxazine pyridinium bromide] (PEHSPB) was prepared by the activated polymerization of 2-ethynylpyridine with 1,3,3-trimethyl-6’-bromohexyloxyspiro[2H]-indol-2,3’-[3H]-naphth[2,1-b][1,4]oxazine without any additional initiator or catalyst. The polymerization reaction was performed in DMF solvent at the temperature of 120 oC. As the polymerization proceeded, the reaction solution became more viscous and black color. The polymer yield and inherent viscosity were 75% and 0.15 dL/g, respectively. The instrumental analysis data on the chemical structure of PEHSPB 6 indicated that the present PEHSPB have a conjugated polymer backbone system with the spiroxazine-hexyl substituents. X-ray diffraction analyses of the polymers indicated that the present polymers are mostly amorphous. The photoluminescence peak is located at 515 nm corresponding to the photon energy of 2.41 eV. Upon UV irradiation, closed spiroxazine form are transformed into the open merocyanine form that reverts back to the colourless spiro form in dark. |
| 저자 | 제갈영순1, 진성호2, 김상율3, 김성훈4, 이원철1 |
| 소속 | 1경일대, 2부산대, 3한국과학기술원 화학과, 4경북대 |
| 키워드 | Conjugated polymer; 2-Ethynylpyridine; polyacetylene; spiroxazine; UV-irradiation |
