Theory of the Mechanism of the Twin Polymerization

在第一个资助期，对一种模型化合物进行了量子化学计算，研究了阳离子孪生聚合的机理。根据计算结果，建立了一个模型，该模型可以确定孪晶聚合过程中对结构形成过程的主要影响因素。通过这种方式，TP 1对在分子水平上对孪生聚合机理细节的基本理解做出了重要贡献。结果得到了质子催化的孪生聚合的详细图像，并确定了对形成纳米复合材料的主要影响因素。前人在孪晶聚合机理理论方面的工作是进一步研究的基础--结合实验结果对孪晶单体和活性物种的性质进行计算，可以揭示复杂的结构-功能相关性和机理细节。在进一步研究的框架内，这一策略将被改进并应用于其他类型的单体和催化剂，用于双元聚合。我们的研究重点是一系列化合物的阳离子双元聚合的计算，这些化合物除了硅和氧，还有硫和硼。这样，将与实验者密切合作收集数据集，以便对关于结构和反应性的统一概念的所有结果进行系统分析。我们的目标是能够通过分析相应单体的结构和反应活性来对孪生聚合过程的结果做出假设。另一个重要的方面是热孪生聚合的计算研究。首先，初步研究表明，理论如何有助于理解热过程的副产品等细节。在下一个资助期，将与实验小组密切合作，设计出一个详细的热孪生聚合机理模型。此外，对一系列单体相互之间的反应性的计算应有助于同时进行孪生聚合的实验研究。

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.