Theory of the Mechanism of the Twin Polymerization

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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.