GOALI: Development and Applications of Multidimensional NMR Methods in Polymer Science

这项提议是为了一个项目，开发先进的多维核磁共振(核磁共振)实验，并将这些方法应用于表征具有重要商业价值的聚合物。在过去的十年里，三重共振三维(3D)核磁共振方法在研究生物大分子的结构方面具有巨大的价值。这些方法在聚合物科学中的使用是相对较新的。最近，关于1-H，13-C和第三个核磁共振活性核X(其中W是19-F，31-P，29-Si或119-Sn)的位移的三重共振3D-核磁共振相关实验已经被描述。然而，许多具有重要商业价值的聚合物材料是基于碳氢化合物的(即，它们只包含1-H和13-C核磁共振活性核)。很明显，需要用核磁共振方法来研究这些材料。该项目的目的是开发一个多维核磁共振实验场地，专门用于表征碳氢化合物合成聚合物。这些实验将用于表征具有重要商业价值的乙烯与α-甲基丙烯酸甲酯、甲基丙烯酸、甲基丙烯酸丁酯和/或一氧化碳的共聚物和三元共聚物的微观结构。这些结构信息将被用来深入了解聚合物中引发、终止、重排和分支形成反应的性质。该项目涉及综合使用学术和产业合作机构的现有独特资源，价值超过1500万美元。它将提供新的分析方法，对聚合物研究人员来说将是有价值的，他们必须表征新材料的结构。从本项目中特定聚合物的分析中获得的信息将对聚合物工程师有用，他们将利用结构信息为工厂过程开发工程模型。这些知识将有助于新材料的开发，有助于改善现有制造材料的性能，并有助于改进聚合物制造工艺的发展。从长远来看，从这项建议中获得的信息和方法将在材料科学行业中普遍使用。

This proposal is for a project to develop advanced multidimensional nuclear magnet resonance (NMR) experiments, and to apply these methods to the characterization of commercially important polymers. For the past decade, triple resonance three dimensional (3D) NMR methods have been enormously valuable for studying the structures of biological macromolecules. The use of these methods in polymer science is relatively new. Recently, triple resonance 3D-NMR correlation experiments relating the shifts of 1-H, 13-C and a third NMR active nucleus X (where W is 19-F, 31-P, 29-Si, or 119-Sn) have been described. However, many commercially important polymeric materials are hydrocarbon based (i.e., they contain only 1-H and 13-C NMR active nuclei). The need for NMR methodology to study these materials is clear. The purpose of this project is to develop a site of multidimensional NMR experiments tailored to the characterization of hydrocarbon-based synthetic polymers. These experiments will be applied to the characterization of the microstructures in commercially important copolymers and terpolymers of ethylene with a-olefins methyl methacrylate, methacrylic acid, butyl methacrylate and/or carbon monoxide. This structure information will be used to gain insight into the nature of initiation, termination, rearrangement and branch-forming reactions in the polymer.The project involves the combined use of existing unique resources, worth more than $15 million, at the academic and industrial partner institutions. It will provide new analytical methods which will be valuable to polymer researchers who must characterize the structures of new materials. The information obtained from the analysis of the specific polymers in this project will be useful to polymer engineers who will use the structure information to develop engineering models for plant processes. This knowledge will aid in the development of new materials, help to improve the properties of existing manufactured materials, and contribute to the development of improvement polymer manufacturing processes. In the long-term, the information and methodology obtained from this proposal will be of general use in the materials science industry.