아세틸렌 유도체들로부터의 전도성 고분자 합성에 관한 연구

학위논문(석사) - 한국과학기술원 : 화학과, 1995.2, [ vii, 53 p. ]A diacetylene, 6-(2-pyridyl)-3,5-hexadiyn-l1-ol(PyHxD, 4) is synthesized and crystallized to obtain a monomer single crystal in order to investigate the effect of pyridyl substituent on topochemical polymerization. PyHxD was polymerized in the presence of water at room temperature although it is impossible to polymerize in bulk state because of its packing pattern. X-ray, UVVIS, Raman, IR spectroscopic studies were utilized to determine the structure of the monomer single crystals and the resulting polymers. (Z)-1-Methoxy-4-phenylbut-1-en-3-yne (MPBEY, 5) was polymerized over $NbCl_5$-based catalysts followed by pyrolysis to obtain new polyacene-based polymers. Poly[(Z)-1-methoxy-4-phenylbut-1-en-3-yne] (poly(MPBEY), 9) has the structure of fully conjugated backbone and completely aromatized on pyrolysis. The brown metathesis polymer was converted into black polyacene-based polymer on pyrolysis. The metathesis polymerization was influenced by substituents directly attached to the acetylene moiety. The polymers were characterized by GPC, FTIR, TGA, NMR, and X-ray diffraction studies.한국과학기술원 : 화학과

아세틸렌 유도체로부터 기능성 고분자의 합성 및 그 성질에 관한 연구

학위논문(박사) - 한국과학기술원 : 화학과, 1998.2, [ xx, 171 p. ](Z)-1-Methoxy-4-phenyl-1-buten-3-yne (MPBEY), 1,4-diphenyl-1-buten-3-yne (DPBEY), 5-(2-pyridyl)-2,4-pentadiyn-1-ol (PyPDO) were polymerized over $NbCl_5$- or $TaCl_5$- based catalysts followed by pyrolysis to obtain graphite-like pyropolymers. The brown metathesis polymer, poly[(Z)-1-methoxy-4-phenyl-1-buten-3-yne] [poly(MPBEY)], has the structure of fully conjugated backbone and was converted into black polyacene-based polymer on pyrolysis. The metathesis polymerization is influenced by substituents directly attached to the acetylene moiety. The structure of the polymers is also influenced by oxygen. The brown metathesis polymer, poly(1,4-diphenyl-1-buten-3-yne) [poly(DPBEY)] was annealed at $250^\circ$C to obtain partially crosslinked polymer which showed 20% increase of carbon residue on pyrolysis over $400^\circ$C than the pyrolyzed poly(1,4-diphenyl-1-buten-3-yne) without annealing. The black metathesis polymer, poly[5-(2-pyridyl)-2,4-pentadiyn-1-ol] [poly(PyPDO)], has the structure of fully conjugated backbone and was converted into polyacene-based polymer having pyridyl pendant group. The pyropolymers prepared by vacuum pyrolysis over 700℃ have nitrogens incorporated into graphene sheets. Four kinds of synthetic carbons were prepared by vacuum pyrolysis of black polyacene-based polymers. The carbonization yields are influenced by the substituents in the precursor polymers. The electrochemical properties of carbons were dependent on the polymers. The relationship between the structure of synthetic carbons and electrochemical behavior was investigated by TEM and CD studies. 3,5-Dinitrobenzoates of poly[1-(n-methoxyphenyl)penta-1,3-diyn-5-ol] [DN-1,n-PMDO, (n = 2,4)] are prepared by the reaction of (1,n)-PMDO (n = 2,4) and 3,5-dinitrobezoyl chloride. DN-1,2-PMDO shows high initial potential and low photoconductivity, while DN-1,4-PMDO shows low initial potential and high photoconductivity. The photoconductivity of DN-1,2-PMDO could be improved by introduc...한국과학기술원 : 화학과