Synthesis of Poly(ethylene Oxide) Rotaxane Networks

9308485合成Pugh双（轮烷）单体和基于氧乙烯重复单元的聚轮烷网络。这是单体和聚合物网络的新拓扑结构。在标准条件下，以及在诱导疏水和疏溶剂相互作用的条件下，对统计和定向穿线进行比较，将提供对大冠醚穿线形成单体和聚合物网络的程度的深入研究。螺纹与悬垂大冠醚的程度将由包含可水解交联的模型体系确定。测定线性聚轮烷前体和水解产物的绝对分子量。先前未确定的线性聚轮烷溶液性质，包括尺寸、形状和二次维里系数，将通过微批光散射测量来确定。双环交联的非共价性质应使网络具有最大的微观迁移率，同时保持宏观形状。因此，这种结构设计应该导致低玻璃化转变温度的非晶网络。聚轮烷网络几乎完全由氧乙烯重复单元组成，这是聚合物电解质中离子迁移的最佳化学结构。最小的拓扑限制可能导致聚合物电解质具有异常高的室温离子电导率。固体聚合物电解质是化学传感器和设备以及薄膜电池应用的兴趣，包括昂贵的用途，如笔记本电脑，起搏器和电动汽车。＊＊＊

9308485 Pugh Bis(rotaxane) monomers and polyrotaxane networks based on oxyethylene repeat units will be synthesized. This is a new topology for both monomers and polymer networks. Comparison of statistical and directed threading under standard conditions, as well as under conditions which induce hydrophobic and solvophobic interactions will provide a through study of the extent of threading the bis(macrocrown ether)s to form monomers and polymer networks. The extent of threaded vs. dangling macrocrown ethers will be determined from model systems containing hydrolyzable crosslinks. Absolute molecular weight of the linear polyrotaxane precursors and hydrolyzed products will be determined. Previously undetermined solution properties of linear polyrotaxanes, including size, shape and second virial coefficients, will be determined by micro-batch light scattering measurements. The non-covalent nature of the bicyclic crosslinks should provide the networks with maximum microscopic mobility, and at the same time, maintain the macroscopic shape. This structural design should therefore result in an amorphous network of low glass transition temperatures. The polyrotaxane networks will be composed almost exclusively of oxyethylene repeat units, which is the optimum chemical structure for ion mobility in polymer electrolytes. The minimal topological constraints could potentially result in polymer electrolytes with unusually high room temperature ionic conductivities. Solid polymer electrolytes are of interest for chemical sensors and devices, and for thin film battery applications, including expensive uses such as laptop computers, pace makers and electric automobiles. ***