Synthesis of Novel Substituted Polyacetylenes and Design of Polymerization Catalysts

本研究涉及新型取代聚乙炔的设计和合成，形成的聚合物的表征及其电光功能的开发。主要研究结果如下：1.新型取代聚乙炔的设计与合成。具有大体积邻位取代基如全氟正己基和(三烷基硅基)甲基的苯基乙炔被聚合以提供新型的高分子量聚合物。作为另一类单体，含有N-咔唑基和三甲基锗基团的二苯基乙炔在TaCl5催化剂的存在下生成了新的聚合物。以3-(N-咔唑基)-1-丙炔、1-苯硫基-1-丙炔、1-丁硫基-2-苯基乙炔等为原料合成了含杂原子的聚乙炔。2.取代聚乙炔的结构与性能基础研究。在可见光红外光谱下，测量了这些聚合物在光激发态下的时间分辨光谱，时间分辨率低于300fs。作为另一项研究，测量了20多种聚合物的紫外光电子光谱，并确定了它们的电离阈值能。这些值对应于最低的激发能。3.取代聚乙炔的电光性质研究。用环取代聚(二苯基乙炔)和聚(1-苯基-1-炔)制备了ITO/聚合物/Mg-In电致发光器件。从器件中观察到绿色和蓝色发光。这些聚合物还显示出光致发光。作为非线性光学性质的研究，测量了9-芳基乙炔共聚物和聚N-咔唑基乙炔的三阶极化率，其值约为聚苯乙炔的10-100倍。这些值可以与紫外可见光谱中的截止波长相关联。

The present study deals with design and synthesis of novel substituted polyacetylenes, characterization of the formed polymers, and development of their electrooptic functions. The results obtained are outlined below.1.Design and Synthesis of Novel Substituted Polyacetylenes. Phenylacetylenes having bulky ortho substituents such as perfluoro-n-hexyl and (trialkylsilyl) methyl groups were polymerized to provide novel high molecular weight polymers. As another type of monomers, diphenylacetylenes with N-carbazolyl and trimethylgermyl groups produced new polymers in the presence of TaCl_5-based catalysts. Further, heteroatom-containing polyacetylenes were obtained from 3- (N-carbazolyl) -1-propyne, 1-phenylthio-1-propyne, 1-butylthio-2-phenylacetylene, and so on.2.Basic Studies on the Structure and Properties of Substituted Polyacetylens. Visiblenear IR,time-resolved spectra of these polymers in photo-excited states were measured with time resolutions below 300 fs. As another study, UV photoelection spectra of more than 20 polymers were measured, and their ionization threshold energies were determined. These values corresponded with the lowest excitation energies.3.Studies on the Electrooptic Properties of Substituted Polyacetylenes. Electroluminescence devices (ITO/Polymer/Mg-In) were fabricated by using ring-substituted poly (diphenylacetylenes) and poly (1-phenyl-1-alkynes). Green and blue luminescences were observed from the devices. These polymers displayd also photoluminescence. As a study of nonlinear optical properties, third-order susceptibilities of 9-anthrylacetylene copolymers and poly (N-carbazolylacetylene) were measured to show values ca. 10-100 times as large as that of poly (phenylacetylene). These values could be correlated with the cutoff wavelengths in UV-visible spectroscopy.