Synthesis of Novel Substituted Polyacetylenes and Design of Polymerization Catalysts

新型取代聚乙炔的合成及聚合催化剂的设计

基本信息

批准号：
07455372
负责人：
MASUDA Toshio
金额：
$ 4.74万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

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.

本研究涉及新型取代的聚乙烯烯的设计和合成，形成的聚合物的表征以及其电流功能的发展。在下面概述了获得的结果。1。设计和合成新型取代的聚乙酰基烯。将具有庞大的矫正取代基（如全氟-n-己基和（试验性甲硅烷基）甲基）聚合聚合以提供新型的高分子量聚合物的苯乙烯。作为另一种类型的单体，具有N-甲基唑基和三甲基甲基基团的二苯基乙烯烯在存在基于TACL_5的催化剂的情况下会产生新的聚合物。此外，从3-（n-甲基唑基）-1-蛋白酶，1-苯基硫代-1-普佩恩，1-丁基Tio-2-苯基乙酰基乙烯等获得含有杂原的聚乙酰基烯。这些聚合物在光兴奋的状态中的粘膜IR，时间分辨的光谱的时间分辨率低于300 fs。作为另一项研究，测量了20多个聚合物的紫外光电传播光谱，并确定了它们的电离阈值能量。这些值与最低的激发能相对应。通过使用环取代的聚（二苯基乙烯烯）和聚（1-苯基-1-烷基）制造电致发光设备（ITO/聚合物/mg-in）。从设备中观察到绿色和蓝色的光度。这些聚合物还显示光致发光。作为非线性光学特性的研究，测量了9-乙酰乙二醇共聚物和聚（N-甲基二基乙炔）的三阶敏感性，以显示值Ca。 10-100倍的大于聚（苯乙烯）。这些值可以与紫外可见光谱中的截止波长相关。