Development of Three-Component Polycondensation Methods and Their Application to One-Step Synthesis of Soluble π-Conjugated Polymers

缩聚技术是合成各种功能材料的重要方法。然而，它过于简单的成键过程往往迫使我们设计复杂的单体来制备具有先进性能和功能的聚合物。作为另一种方法，我们一直致力于新型三组分缩聚工艺的开发和应用。本研究项目开发了一类新型的三组分缩聚工艺，并将其应用于合成具有在有机溶剂中的溶解性等高级功能的π共轭聚合物。例如，通过卤代芳烃与具有官能团的亲核试剂进行三组分缩聚，合成了具有独特功能的聚芳烃-乙烯S。因此，根据亲核试剂的性质，可以生产具有独特功能的π共轭聚合物。在Suzuki-Miyaura偶联反应中，以乙炔或降冰片二烯为第三组分，可建立一种新的三组分缩聚工艺。从这些聚合体系中，可以从简单的单体合成具有新的主链结构单元的π共轭聚合物。一些合成的聚合物被发现具有独特的功能，如溶剂变色发光性能。

Polycondensation technique is a quite important synthetic method for various functional materials. Nevertheless, its too simple bond formation process often forces us to design complicated monomers for preparation of polymers with advanced properties and functions. As an alternative approach, we have been working on the development and applications of novel three-component polycondensation processes. In this research project, the development of a new class of three-component polycondensation processes and their applications to the synthesis of π-conjugated polymers with advanced functions such as solubility in organic solvents were studied.For example, the synthesis of poly(arylene-vinylene)s having unique functions were prepared by the three-component polycondensation of haloarylallenes and nucleophiles having functional moieties. Consequently, π-conjugated polymers having unique functions could be produced depending on the nature of the nucleophiles. Also, a new three-component polycondensation processes could be established by use of acetylenes or norbornadiene as third components in the coupling processes such as the Suzuki-Miyaura coupling reaction. From these polymerization systems, π-conjugated polymers having new main chain structural units could be prepared from simple monomers. Some of the resulting polymers were found to exhibit unique functions such as solvatochromic luminescent properties.