Experimentelle und theoretische Untersuchungen zur Ringöffnungspolymerisation von nachwachsenden cyclischen Estern durch N-Donor-Zinkkomplexe

N-供体锌配合物开环聚合可再生环酯的实验与理论研究

• 批准号: 174939012
• 负责人: Professorin Dr. Sonja Herres-Pawlis
• 金额: --
• 依托单位: Lehrstuhl für Bioanorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2012-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/174939012?language=en
• 关键词: Experimentelle; und; theoretische; Untersuchungen; zur

The use of polymer materials enables our modern way of life. Due to the inexorable depletion and exploding costs of fossil resources and growing landfill sites, the need for ecological polymers has never been more exigent. Our society requires new advanced materials which can be produced by sustainable versatile tools. We target the ultimate catalyst which marries the two complementary polymerisation methods of ring-opening polymerisation (ROP) and atom transfer polymerisation (ATRP). Both polymerisation methods are essential techniques for the sustainable synthesis of modern block-copolymers as intelligent high-performance materials. This innovative union has not been realised yet although urgently needed for the general substitution of petrochemical plastics. The superior catalyst is based on iron complexes since this element offers sufficient Lewis acidity (for ROP) and one-electron redox chemistry (for ATRP) by being at the same time sustainable, biocompatible and available. Until now, there is a significant lack of understanding of the mechanisms using iron complexes.In this project, we aim to develop an iron(II)-based high-performance ATRP catalyst and an iron(III)-based high-performance ROP catalyst - both combined within one single system. The monomer scope for both methods will be expanded towards novel renewable monomers. We will first address both methods separately for a fundamental understanding. The catalyst development follows intelligent design principles with theoretical feedback from the first catalyst generation. Then, we design a dual-functional catalyst where the redox-control between both oxidation states allows to switch between the polymerisation methods. On the larger perspective, multi-component block-copolymers are built up for modern polymer architectures. In summary, we target to develop by comprehensive design the ultimate sustainable polymerisation catalyst as multifunctional redox-controlled tool.

高分子材料的使用使我们的现代生活方式成为可能。由于化石资源的不可阻挡的消耗和爆炸性的成本以及不断增长的垃圾填埋场，对生态聚合物的需求从未如此迫切。我们的社会需要新的先进材料，这些材料可以通过可持续的多功能工具生产。我们的目标是最终的催化剂，它结合了开环聚合（ROP）和原子转移聚合（ATRP）这两种互补的聚合方法。这两种聚合方法都是可持续合成现代嵌段共聚物作为智能高性能材料的基本技术。这种创新的结合尚未实现，尽管迫切需要替代石化塑料。该上级催化剂基于铁络合物，因为该元素提供足够的刘易斯酸度（用于ROP）和单电子氧化还原化学（用于ATRP），同时具有可持续性、生物相容性和可用性。目前，对于铁络合物的作用机理还不甚了解。本课题旨在开发一种铁（II）系高性能ATRP催化剂和一种铁（III）系高性能ROP催化剂，并将两者结合在一个系统中。这两种方法的单体范围将扩大到新的可再生单体。我们将首先分别讨论这两种方法，以获得基本的理解。催化剂的开发遵循智能设计原则，并从第一代催化剂中获得理论反馈。然后，我们设计了一种双功能催化剂，其中两种氧化态之间的氧化还原控制允许在聚合方法之间切换。从更大的角度来看，多组分嵌段共聚物是现代聚合物结构的基础。总之，我们的目标是通过综合设计开发最终的可持续聚合催化剂作为多功能氧化还原控制工具。