Poly(1-phenylpenta-1,3-diyn-5-ol) (PPDO), prepared by $NbCl_5$/$(n-Bu)_4Sn$ catalysed metathesis of PDO, was converted into a graphite-like structure with high electrical conductivity in the absence of dopants by heat treatment at 800℃under vacuum. Poly(2,4-hexadiyn-1,6-diol) (PHDO), prepared by $NbCl_5$/$(n-Bu)_4Sn$ catalyzed metathesis of HDO, was pyrolyzed at various temperatures and electrical and structural properties of resulting polymers were investigated by FT-IR, Laser Raman, CP/MAS $^{13}C-NMR$ and X-ray diffraction methods. The polymer obtained by pyrolysis of PHDO at 800℃ showed a conductivity of about 10 S/cm at room temperature. The structure of the polymer seems to be a graphite-like crystal consisting of condensed aromatic layers.
Poly[1-(2-methoxyphenyl)penta-1,3-diyn-5-ol] [(1,2)-PMDO] was prepared by $NbCl_5$/$(n-Bu)_4Sn$ catalyzed metathesis of (1,2)-MDO followed by spin-casting from MC solvation. Thin films of resulting polymers were pyrolyzed at various temperatures. UV, IR, and Raman spectroscopies were employed to investigate the chemical structure of the films during pyrolysis. The electrical conductivity of films can be varied over several decades by changing the final temperature of cabonization.
Poly[1-(2-methoxyphenyl)penta-1,3-diyn-5-ol] [(1,2)-PMDO], was prepared by $NbCl_5$/$(n-Bu)_4Sn$ catalyzed metathesis. The 2:3 (1,2)-PMDO/PMMA (w/w) film showed a conductivity of about $10^{-3}$ S/cm after $FeCl_3$ doping. Third order nonlinear optical susceptibility ($\chi^3$) of (1,2)-PMDO, evaluated from third harmonic generation by Maker fringe method, showed $1.03\times10^{-13}$ esu.
2,4-Hexadiyn-1,6-diol (HDO) was polymerized on a glass and silicon plate by chemical vapor deposition without transition metal catalyst to form a homogeneous thin film. Structural properties of the films were investigated by FT-IR, UV-visible, fluorescence, X-ray diffraction, and XPS spectroscopic analyses. The CVD-polymerized HDO (CVD-PHDO) films were found to give a chemical structure different from that of metathesis polymerized HDO (metathesis-PHDO), showing a polyacene-based structure but no polyene structure with acetylenic side groups.
PDO와 HDO의 선택적인 메타세시스 1,2 중합에 의해 생성된 PPDO와 PHDO를 파이로리시스하면 곁사슬의 탄소 탄소 3중 그룹의 고리화 반응에 의해 흑연과 비슷한 구조의 물질이 생성되는데 이물질은 화학적 도핑이 필요없이 높은 전기 전도도를 띤다. 특히 PHDO-800은 높은 다공성과 전기 전도도로 인해 2차 전지의 전극 물질로 응용할 수 있는 가능성을 보이고 있다.
PPDO와 PHDO가 유기용매에 녹지 않아 1-phenyl-1,3diacetylenes의 phenyl ring에 methoxy기를 도입함으로서 생성된 (1,2)-PMDO는 극성 유기용매에 녹는다. (1,2)-PMDO와 PMMA를 MC에 녹여 생성된 브렌드 중합체 필름은 바람직한 기계적 성질을 띠며 특히 (1,2)-PMDO와 PMMA를 2 : 3 무게비로 생성된 필름은 $FeCl_3$로 도핑 후 $10^{-3}$ S/cm의 전도도를 띤다. 또한 (1,2)-PMDO는 THG (Third Harmonic Generation) 측정 방법에 의해 $1.03\times10^{-13}$ esu의 $\chi^3$ 값을 갖는다.
HDO를 Chemical Vapor Deposition 방법에 의해 중합된 필름은 곁사슬에 -$CH_2OH$기를 가지고 있으며 triple bond는 가지고 있지 않다. 이 CVD-중합은 두 triple bond가 열리면서 일어나며 HDO의 메타세시스 중합과 다르게 polyacene-based 구조의 물질을 형성한다. UV 와 fluorescence spectra에 의해 CVD-PHDO의 구조는 확장된 π-conjugated 계이며 LED (Light Emitting Device)로서의 응용 가능성을 보인다.