Molecular investigation of the swelling behaviour of polymer model networks

该项目由两部分组成，分别侧重于更好地理解聚合物网络中的缠结和可逆键。在项目的第一部分中，将开发一个合适的模型，用于仅由缠结组成的理想网络的变形。这是基于滑管模型，奥林匹克凝胶的溶胀的先前结果，以及理想的滑环凝胶和奥林匹克凝胶的变形和溶胀的额外模拟数据，这是由当前项目贡献的。为了更好地理解这些网络的弹性和缠结的相互作用以及在溶胀和变形过程中环糊精沿着链的受限扩散，将缠结网络的该模型扩展到具有大量环糊精的真实的滑环凝胶的模型。为此，应使用一系列奥林匹克凝胶和/或滑动环凝胶与增加量的额外共价交联来研究连接和缠结对溶胀和变形的非亲和性的相互影响。这些研究的目标是建立一个定量模型，也为非仿射贡献的变形和溶胀的传统的聚合物networks.The可逆键的重组动力学的理论将在该项目的第二部分扩展到包括应力诱导断裂的键和缠结网络。部分可逆的模型网络的变形和能量耗散的模拟的目标是量化的集体重排和应力松弛的结果断裂键，并开发这个过程的模型。应使用两类模型网络（沿连接点之间的链沿着的粘着物和在星星臂或支化聚合物末端的粘着物）分析和理解分子构建块的结构对部分可逆网络松弛的影响。

The project consists of two parts that focus on a better understanding of entanglements and reversible bonds in polymer networks, respectively.In the first part of the project, a suitable model shall be developed for the deformation of ideal networks that consist solely of entanglements. Thiss occurs based upon slip tube models, preceeding results on the swelling of Olympic gels, and additional simulation data on the deformation and swelling of ideal slide-ring gels and Olympic gels, which are contributed by the current project. This model for networks of entanglements shall be extended to model real slide-ring gels with a multitude of cyclodextrine in order to better understand the elasticity of these networks and the interplay of entanglements and the confined diffusion of cyclodextrine along the chains during swelling and deformation. To this end, the mutual influence of junctions and entanglements on the non-affinity of swelling and deformation should be investigated using a series of Olympic gels and/or slide-ring gels with an increasing amount of additional covalent cross-links. It is the goal of these investigations, to develop a quantitative model also for the non-affine contributions to deformation and swelling of conventional polymer networks.The theory about the recombination dynamics of reversible bonds shall be extended in the second part of the project to incorporate stress-induced breakage of bonds and entangled networks. The simulation of the deformation and energy dissipation of partially reversible model-networks has the goal to quantify the collective rearrangements and stress relaxation in consequence of a breaking bond and to develop a model for this process. The impact of the architecture of the molecular building blocks on the relaxation of partially reversible networks shall be analyzed and understood using two classes of model networks (stickers along the chains between junctions and stickers on the ends of star arms or branched polymers).