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Photo-Induced Polymerization Reactions: Quantitative Information via Mass Spectrometry and Femtosecond Pump-Probe Absorption Studies

光诱导聚合反应：通过质谱和飞秒泵浦探针吸收研究获得定量信息

基本信息

批准号：
158927932
负责人：
Professor Dr. Christopher Barner-Kowollik
金额：
--
依托单位：
Institut für Physikalische Chemie (IPC)
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 2015-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/158927932?language=en
关键词：
Photo Induced Polymerization Reactions Quantitative

项目摘要

The current extension request builds on the work of the past 2.5 years funded by the DFG on the topic of Quantifying the Reactivity of Photolytically Generated Radicals Towards Vinylic Monomers via Electrospray Ionization Mass Spectrometry (ESI-MS), where the foundation was laid for achieving an in-depth quantitative understanding of photo-initiation processes via the provision of relative net initiation ratios associated with individual radical fragments originating from various photoinitiators. In the course of the research we found unexpectedly that femtosecond spectroscopy in combination with the pulsed laser polymerization size-exclusion chromatography ESI-MS (PLP-SEC-ESI-MS) experiments yield not only insights into the relative net efficiency of a radical fragment, but also allows to correlate the observed net efficiencies with the internal energy distribution within the excited molecule, i.e. the efficiency of the singlet to triplet intersystem crossing after laser excitation. The original grant has led to the study of 9 initiation systems leading to 4 peer-reviewed research outputs (as well as additional forthcoming manuscripts) that highlight the power of our combined experimental approach to for the first time generate quantitative knowledge about net efficiencies of photoinitiators with their internal energy dissipation channels. Within the requested extension project, we now wish to exploit our combined experimental set-up in a collaborative project between the KIT Polymer and Physical Chemistry institutes. The key aim is the quantitative determination of the relative net initiation efficiency via the now established PLP-SEC-ESI-MS technique for a wide range of radical fragments coupled with the quantitative understanding of the intersystem crossing behavior of the constituting initiator molecules, to arrive at a map of origin dependent radical fragment initiation efficiencies. We believe that a unique opportunity exists to for the first time provide a full and comprehensive understanding of final polymer end group distribution of photolytically generated radical fragments with the structure dependent internal energy conversion within the photoinitiators.

目前的延期请求建立在DFG资助的过去2.5年的工作基础上，该工作的主题是通过电喷雾电离质谱法（ESI-MS）量化光解产生的自由基对乙烯单体的反应性，在那里奠定了基础，实现了深入的定量了解照片-通过提供与源自各种光引发剂的单个自由基片段相关的相对净引发比来引发过程。在研究过程中我们意外地发现飞秒光谱与脉冲激光聚合体积排阻色谱电喷雾质谱联用技术相结合（PLP-SEC-ESI-MS）实验不仅产生对自由基片段的相对净效率的洞察，而且还允许将观察到的净效率与激发分子内的内部能量分布相关联，即激光激发后单重态到三重态系间交叉的效率。最初的资助导致了9个引发系统的研究，导致4个同行评审的研究成果（以及其他即将出版的手稿），突出了我们的综合实验方法的力量，首次产生了关于光引发剂净效率的定量知识，其内部能量耗散通道。在请求的扩展项目中，我们现在希望在KIT聚合物和物理化学研究所之间的合作项目中利用我们的联合实验装置。主要目的是通过现在建立的PLP-SEC-ESI-MS技术定量测定广泛的自由基片段的相对净引发效率，并定量了解构成引发剂分子的系统间交叉行为，以获得来源依赖性自由基片段引发效率的图。我们认为，存在一个独特的机会，第一次提供一个完整和全面的了解最终的聚合物端基分布的光解产生的自由基片段与结构依赖的内部能量转换内的光引发剂。