Theory of the Mechanism of the Twin Polymerization

在第一个资助期内，对模型化合物进行了量子化学计算，以研究阳离子孪晶聚合的机理。从计算的结果中，一个模型已被参数化，允许确定的主要影响过程中的双聚合的结构形成。这样，TP 1在分子水平上对孪晶聚合的机理细节的基本理解做出了重大贡献。因此，质子催化的双聚合的详细图片已被获得，并已确定的纳米复合材料的形成的主要影响。一系列的联合论文表明了理论和实验之间的良好合作和协同作用。先前关于孪晶聚合机理理论的工作是进一步研究的基础-孪晶单体和活性物种的性质计算与实验结果相结合，可以解开复杂的结构-功能相关性和机理细节。在进一步研究的框架内，这一策略将被细化并应用于其他类型的单体和类型的双polymerization.The我们的研究重点是计算的阳离子双polymerization的一系列化合物，其中包含，除了硅和氧，硫或硼。通过这种方式，将与实验人员密切合作收集数据集，以便对所有结果进行系统分析，统一结构和反应性的概念。其目的是通过分析相应单体的结构和反应性，对孪晶聚合过程的结果做出假设，另一个重要方面是对热孪晶聚合过程的计算研究。首先，初步研究表明，理论可以帮助理解细节，如热过程的副产品。在下一个资助期内，将与实验组密切合作，设计一个详细的热孪生聚合机理模型。此外，一系列单体之间的反应性的计算应允许帮助同时双聚合的实验研究。

In the first funding period, quantum chemical calculations on a model compound have been used to investigate the mechanism of the cationic twin polymerization. From the results of the calculations, a model has been parametrized that allowed to identify the major influences on the process of structure formation during the twin polymerization. This way, TP 1 contributed significantly to the basic understanding of mechanistic details of the twin polymerization at the molecular level. As a result, a detailed picture of the proton catalyzed twin polymerization has been obtained and the major influences on the formation of a nanocomposite have been identified. A series of joined papers demonstrates the good cooperation and synergy between theory and experiment.The previous work on the mechanistic theory of the twin polymerization is the foundation for further studies - the calculation of properties of twin monomers and active species in combination with experimental findings allows to unravel complex structure-functionalitly correlations and mechanistic details. In the framework of further studies this strategy will be refined and applied to other classes of monomers and types of catalysis for the twin polymerization.The focus of our studies are computations for the cationic twin polymerization of a series of compounds which contain, besides silicon and oxygen, sulfur or boron. This way, a data set will be collected in close collaboration with experimentalists, that allows for a systematic analysis of all results with respect to unifying concepts of structure and reactivity. The goal is, to be able to make assumptions on the outcome of a twin polymerization process by analysis of the structure and reactivity of the corresponding monomer.A further important aspect is the computational study of the thermal twin polymerization. First preliminary studies have shown how theory can aid in understanding details like side products of the thermal process. In the next funding period, a detailed mechanistic model for the thermal twin polymerization will be devised in close collaboration with the experimental groups. Furthermore, calculations on the reactivity of a series of monomers among each other should allow to aid the experimental investigations on the simultaneous twin polymerization.