Self-organized films of supramolecular coordination polymers and their materials transport properties

配位吸附金属离子和以配体为取代基的聚合物(多配位配体)将被用来构建配位聚合物网络的超薄膜和分离膜，并研究它们的材料输运性质。到目前为止，关于配位聚合物用作分离膜的知识还很少。这项工作的起点将是合成合适的以配体为取代基的聚合物(多聚配体)。制备将作为乙烯基单体和丙烯酸酯单体的自由基共聚合进行，这是含有配体基团的共聚单体(A)之一。另一种共聚单体(B)将改变，以形成具有不同亲水性、电荷以及对pH、温度或电位敏感的行为的共聚物。将研究沉积的薄膜的结构特性(光学吸收、薄膜厚度、形态、金属含量)。这些膜将通过将各种共聚物和金属盐逐层吸附在多孔性基质上而制备。通过改变共聚物的共聚单体比A：B来改变膜的网络密度。在扩散渗析和纳滤条件下，通过测量盐和中性分子在水溶液和有机溶液中的渗透速率来研究材料的传输。将研究不同网络密度的膜。含有阳离子或阴离子共聚单元的聚合物的膜应该能够充当阳离子或阴离子交换剂。这将在研究电渗析条件下电解质水溶液的脱盐和脱酸的例子中得到证明。还将研究制备可切换膜的可能性。为此，将研究含有氧化还原活性成分或pH和温度敏感序列的共聚物的膜。对于这些膜，将试图通过改变氧化状态、pH或温度来影响其通量和选择性。

Coordinative layer-by-layer adsorption of metal ions and polymers with ligands as substituents (polytopic ligands) will be used to build up ultrathin films and separation membranes of coordination polymer networks and to study their materials transport properties. Up to now there is little knowledge about the use of coordination polymers as separation membranes. Starting point of the work will be the synthesis of suitable polymers with ligands as substituents (polytopic ligands) The preparation will be carried out as radical copolymerization of vinyl- and acrylic monomers, one of the comonomers (A) containing a ligand group. The other comonomer (B) will be varied such that copolymers with different hydrophilic properties, charge, and pH-, temperature- or potential-sensitive behaviour are formed.The deposited films will be investigated on their structural properties (optical absorption, film thickness, morphology, metal content). The membranes will be prepared upon layer-by-layer adsorption of various copolymers and metal salts on porous substrates. The network density of the membranes is varied by changing the comonomer ratio A:B of the copolymer. The materials transport will be investigated by measuring the permeation rates of salts and neutral molecules in aqueous and organic solution under conditions of diffusion dialysis and nanofiltration. Membranes of different network density will be studied. Membranes containing polymers with cationic or anionic comonomer units should be able to act as cation or anion exchangers. This will be proven studying the example of desalination and deacidification of aqueous electrolyte solutions under electrodialysis conditions. The possibility to prepare switchable membranes will also be studied. For this purpose membranes containing copolymers with redox-active components or pH- and temperature-sensitive sequences will be studied. For these membranes it will be tried to influence their flux and selectivity by changing the state of oxidation, the pH or the temperature.