Alternative Resting States of Olefin-Polymersization Catalysts - Detection of Relevant Reaction Channels by UV/vis, EPR- and NMR-Spectroscopic Methods

烯烃聚合催化剂的替代静止状态 - 通过 UV/vis、EPR 和 NMR 光谱方法检测相关反应通道

• 批准号: 135024452
• 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: 2009
• 资助国家: 德国
• 起止时间: 2008-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/135024452?language=en
• 关键词: Alternative; Resting; States; Olefin; Polymersization

Key for the preparation of new polyolefin materials is tailoring of their microstructure – and thus of polymer properties – via the catalyst. Novel catalysts provide access e.g. to block copolymers. An issue which is rather poorly understood for individual systems, however, is the nature of the different metal species actually present under realistic reaction conditions, i.e. in the presence of large amounts of monomer. The project aims at in-situ identification and quantification of species distribution, e.g. of resting states, in selected metalloceneand post-metallocene-based olefin-polymerization catalysts by adapting existing spectroscopic methods – mainly UV/vis, EPR and NMR techniques – toward this goal. Prof. Mecking contributes expertise for a novel living and stable post-metallocene polymerization catalyst particularly suited for such studies. Prof. Brintzinger brings to this project his experience in metallocene reaction chemistry, and Prof. Möller will contribute to its methodological side. Cooperation of our Russian partners at the Boreskov Institute of Catalysis with the group of Prof. Brintzinger, which has led to a series of joint publications during the last years, is to be further developed and applied to post-metallocene systems.

制备新型聚烯烃材料的关键是通过催化剂调整其微观结构-从而调整聚合物性能。新型催化剂提供了例如获得嵌段共聚物的途径。然而，对于单个体系理解相当少的问题是在实际反应条件下，即在大量单体存在下实际存在的不同金属物质的性质。该项目旨在通过调整现有的光谱方法--主要是UV/维斯、EPR和NMR技术--实现这一目标，对选定的基于烯烃和后茂金属的烯烃聚合催化剂中的物种分布（例如静止状态）进行原位鉴定和量化。Mecking教授为特别适合此类研究的新型活性和稳定的后茂金属聚合催化剂贡献了专业知识。Brintzinger教授为该项目带来了他在茂金属反应化学方面的经验，Möller教授将为其方法学方面做出贡献。我们在博雷斯科夫催化研究所的俄罗斯合作伙伴与Brintzinger教授团队的合作在过去几年中产生了一系列联合出版物，该合作将进一步发展并应用于后茂金属系统。

项目成果

The origin of living polymerization with an o-fluorinated catalyst: NMR spectroscopic characterization of chain-carrying species.

• DOI: 10.1002/chem.201102408
• 发表时间: 2012-01
• 期刊: Chemistry
• 作者: H. Möller;M. Baier;S. Mecking;E. P. Talsi;K. Bryliakov

Formation of trivalent zirconocene complexes from ansa-zirconocene-based olefin-polymerization precatalysts: an EPR- and NMR-spectroscopic study.

由柄型二茂锆基烯烃聚合预催化剂形成三价二茂锆配合物：EPR 和 NMR 光谱研究

• DOI: 10.1021/ja403170u
• 发表时间: 2013
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Lenton;Taylor N;Bercaw;John E;Panchenko;Valentina N;Zakharov;Vladimir A;Babushkin;Dmitrii E;Soshnikov;Igor E;Evgenii P;Brintzinger;Hans H.
• 通讯作者: Hans H.

Formation and evolution of chain-propagating species upon ethylene polymerization with neutral salicylaldiminato nickel(II) catalysts.

• DOI: 10.1002/chem.201301037
• 发表时间: 2013-08
• 期刊: Chemistry
• 作者: I. Soshnikov;N. V. Semikolenova;V. Zakharov;H. Möller;Franz Olscher;Anna Osichow;I. Göttker-Schnettmann;S. Mecking;E. P. Talsi;K. Bryliakov