AM2Net Advanced Macromolecular Materials By Transition Metal Catalysis; Group 2: "Post Metallocene Catalysis"; Functional Polyolefin Architectures via Post-Metallocene Catalysis

烯烃单体的乳液聚合是最重要的，也是通用的聚合方法之一。得到了聚合物晶格，即聚合物微粒的稳定的水分散体，尺寸范围为50 ~ 1000 nm。到目前为止，聚合物乳液的工业生产完全是通过自由基过程。然而，乳液催化聚合正受到越来越多的关注。目前，对于适合于烯烃水聚合的特殊晚期过渡金属配合物对水的反应性，还没有系统的认识。感兴趣的基本反应步骤包括：1)水与烯烃单体与金属中心的相对结合。2)金属烷基键的水解。3)金属结合单体对水的反应性。这些反应将进行实验研究，特别是通过核磁共振监测和通过研究催化寡聚和聚合反应。与水杨醛二胺配体的中性镍（II）配合物（已知非常适合合成高分子量聚乙烯分散体）和阳离子钯二胺配合物（特别适合作为模型化合物）将被采用。齐格勒小组将在密切合作下同时模拟这些反应，并在实验和理论研究之间进行持续反馈。

Emulsion polymerization of olefinic monomers is one of the most important, and also versatile polymerization processes. Polymer latices are obtained, i.e. stable aqueous dispersions of polymer microparticles in the size range of 50 to 1000 nm. To date, polymer latices are produced industrially by free radical processes exclusively. However, catalytic polymerization in emulsion is receiving strongly increased interest. Currently, little systematic knowledge of the reactivity of the particular late transition metal complexes suited for aqueous olefin polymerization towards water exists. Fundamental reaction steps of interest comprise: 1) the relative binding of water vs. olefinic monomers to the metal centers. 2) hydrolysis of metal alkyl bonds. 3) the reactivity of metal-bound monomer towards water. These reactions will be investigated experimentally, especially by NMR monitoring and by study of catalytic oligomeriation and polymerization reactions. Neutral nickel(II) complexes with salicylaldimine ligands, known to be well suited for the synthesis of high-molecular-weight polyethylene dispersions, and cationic palladium diimine complexes, which are particularly well suited as model compounds will be employed. In a close collaboration these reactions will be modelled by the Ziegler group at the same time, with a continuous feedback between experimental and theoretical studies.