Dispersions of conjugated polymers from catalytic polymerization in aqueous systems

共轭聚合物受到学术界和应用领域的广泛关注。它们对于例如显示器或有机太阳能电池中的光电子学具有重要的技术意义。虽然聚合物纳米粒子的水分散体已被广泛研究，但具有碳氢化合物骨架的共轭聚合物的分散体，如聚炔烃、聚对苯二烯和聚苯乙烯类的分散体至今仍难以捉摸。然而，他们是一个有吸引力的目标。除了对它们的制备和性质有根本的兴趣外，它们还可以解决加工问题，这些问题在聚合物多层结构的制备中至关重要。在含大分子膦配体的阳离子钯催化剂上，研究了乙炔和取代烯烃在水乳液中的催化链生长聚合。我们将研究A2与B2单体的催化分步聚合，以及AB单体通过Suzuki偶联得到胶体稳定的聚对苯撑分散体。本论文的研究目的是通过非环二烯歧化聚合法制备聚对苯乙烯类分散体。将针对反应混合物的不同初始胶体状态(大乳液、微乳液和微乳液)以及水溶和表面活性单体研究不溶于水的单体。将使用适当的亲油性和水溶性催化剂。将对聚合物微结构进行表征。聚合物纳米粒子的大小和结构将通过透射电子显微镜和原子力显微镜进行表征。我们将研究薄膜的形成和结构与温度的关系，并初步研究其物理性质。

Conjugated polymers are subject to broad academic and applications-oriented interest. They are technologically important for, e.g., optoelectronics in displays or organic solar cells. While aqueous dispersions of polymer nanoparticles in general have been widely studied, dispersions of conjugated polymers with a hydrocarbon carbon backbone, like polyalkynes, poly(pphenylenes), and poly(phenylene vinylenes) are elusive to date. However, they are an attractive target. Beyond fundamental interest in their preparation and properties, they could resolve issues of processing, which are critical e.g. in the preparation of polymer multilayer structures. Catalytic chain-growth polymerization of acetylene and substituted alkynes in aqueous emulsion to afford polyalkyne dispersions will be investigated with cationic palladium catalysts with bulky phosphine ligands. Catalytic step-growth polymerization of A2 with B2 monomers, and of AB monomers by Suzuki coupling to colloidally stable poly(p-phenylene) dispersions will be investigated. The preparation of dispersions of poly(phenylene vinylenes) by acyclic diene metathesis polymerization with ruthenium alkylidenes is aimed at. Waterinsoluble monomers will be studied for different initial colloidal states of the reaction mixtures (macro-, mini-, and microemulsions), as well as water-soluble and surface active monomers. Suitable lipophilic and water-soluble catalysts will be employed. Polymer micro structures will be characterized. Sizes and structures of the polymer nanoparticles will be elucidated by TEM and AFM. The formation of thin films and their structures will be investigated temperature-dependent, and their physical properties studied preliminarily.