Adaptive Polymergele mit kontrollierter Netzwerkstruktur

两亲性聚合物网络(ACN)由疏水和亲水的聚合物构建块组成，形成一种常见的渗流网络结构，能够在水和有机介质中膨胀。这种两亲性的膨胀性导致了对亲水性、疏水性和两亲性物质的溶剂敏感型粘弹性和渗透性。两者都可以作为软性隐形眼镜、可切换电池衬底或抗菌涂层等多种应用的基础。然而，聚合物网络的纳米结构和微观结构决定了其对溶剂敏感的粘弹性和渗透膜选择性，而聚合物网络的纳米结构和微观结构又因选择性介质中团簇和部分坍塌结构域的存在而变得更加复杂。我们的研究计划旨在提供这些结构和性能之间的定量关系。为了达到这一目标，我们从模型网络结构开始，就像酒井和柴山的四重聚乙二醇法所获得的那样，我们将对ACN采用这种方法。为了使其真正有意义，我们将实现两种不同的ACN。一类由共价和永久连接的构建块组成；另一类由离子连接和瞬时可逆连接的构建块组成。前者的纳米结构和微观结构既由实验中当前膨胀状态的条件决定，也由网络形成时刻的条件决定，而后者仅由测量条件决定。通过比较这两类互补的ACN，可以清楚地认识到在网络渗透过程中形成的网络不规则性的影响。在此基础上，我们将确定网络构建块的化学和拓扑组成、它们的化学计量比以及进一步的反应参数(如浓度、温度、反应性和粘度)对得到的共价交联的ACN网络结构的影响，以及这种结构是如何通过其相对亲性部分的选择性膨胀和崩溃而进一步复杂化的。特别是，我们将确定在什么参数空间中将存在大的、潜在的渗流域，以及选择性介质中折叠的构建块的聚集数量是如何的。在这些结构模型的基础上，我们将重点研究网络结构及其粘弹性力学和凝胶样品表面和整体的渗透选择渗透率之间的相互作用。所有这些研究都将从实验和理论两个角度进行。我们的总体目标是在实验和理论之间进行强烈的反馈，目的是推导出ACN的定量结构-性质关系，作为在此基础上合理设计软材料的基础。

Amphiphilic conetworks (ACN) consist of hydrophobic and hydrophilic polymer building blocks that form a common percolated network structure able to swell in both water and organic media. This amphiphilic swellability leads to solvent-sensitive viscoelasticity and permeability for hydrophilic, hydrophobic, and amphiphilic substances. Both can serve as a basis for versatile applications such as soft contact lenses, switchable cell substrates, or antimicrobial coatings. The solvent-sensitive viscoelastic and perm-selective properties, however, are determined by the polymer network nano- and microstructure, which, in turn, is further complexed by the presence of clusters and partially collapsed domains in selective media. Our research initiative aims at delivering quantitative relations between these structures and properties. To reach that goal, we start from model-network structures as obtained by Sakai's and Shibayama's tetra-PEG approach, which we will adopt for ACN. To make this truly meaningful, we will realize two different classes of ACN. One class consists of covalently and permanently connected building blocks; another class consist of ionically and transient-reversibly connected building blocks. Whereas the nano-and microstructures of the first are determined by both the conditions during a current state of swelling in an experiment as well as the conditions during the moment of network formation, the latter are determined only by the conditions at measurement. Comparison of both these complementary classes of ACN allows the impact of network irregularity as formed during the network percolation to be clearly recognized. On this basis, we will determine the impact of the chemical and topological constitution of the network building blocks, their stoichiometric ratio, and further reactions parameters such as concentration, temperature, reactivity, and viscosity on the resulting network structure of covalently interlinked ACN, and how this structure is further complexed by selective swelling and collapse of their oppositely philic parts. In particular, we will determine in what parameter space large, potentially percolated domains will be present and how the aggregation number of the collapsed building blocks in selective media is. On the basis of these structural models, we will focus on the interplay of the network structures and their viscoelastic mechanics and perm-selective permeability both at the gel-specimen surface and in their bulk. All these studies will be conducted both from experimental and theoretical perspectives. It is our overall goal to undergo intense feedback between experiment and theory, with the aim to derive quantitative structure-property relations for ACN as a basis for rational design of soft materials based on them.