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

AM2Net 过渡金属催化先进高分子材料；

• 批准号: 5372557
• 负责人: Professor Dr. Stefan Mecking
• 金额: --
• 依托单位: Arbeitsgruppe Chemische Materialwissenschaft
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2002
• 资助国家: 德国
• 起止时间: 2001-12-31 至 2012-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/5372557?language=en
• 关键词: AM2Net; Advanced; Macromolecular; Materials; Transition

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.

烯烃单体的乳液聚合是最重要，多功能的聚合过程之一。获得聚合物乳酸，即在50至1000 nm的尺寸范围内的聚合物微粒的稳定水分散体。迄今为止，聚合物乳酸是由自由基工艺专门生产的。但是，乳液中的催化聚合正在获得强烈增加的兴趣。当前，对适用于烯烃聚合水的特定晚期过渡金属复合物的反应性的系统知识很少。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）金属结合的单体对水的反应性。这些反应将进行实验，特别是通过NMR监测以及研究催化寡聚和聚合反应。中性镍（II）配合了水杨甲基胺配体，已知非常适合合成高分子量的聚乙烯分散剂，以及阳离子二亚胺复合物，这些复合物将特别适合作为模型化合物。在密切合作中，这些反应将由齐格勒组同时建模，并在实验研究和理论研究之间进行连续反馈。