Synthesis and Properties of Novel Polymers with Rotaxane Architectures

小行星9320196吉布森 “聚轮烷”由物理地穿线到线性大分子上的环状分子组成，在环状物和线性主链之间没有共价键;大的端基可以装配到链端以防止大环通过脱线损失。 聚轮烷在溶解性、固态结构和相变方面表现出独特的性质。 在这项研究中，从根本上理解的线程的环状分子的线性物种的因素，如性质的两个组件（大小，刚度，结构相似性），溶剂（构象方面的两个组件）和温度。 许多新的聚轮烷将被合成。 衍生自聚合物大环的轮烷，主链和侧链，将用于共混物增容和粘度增强。 具有轮烷表面的树枝状聚合物将允许定制这些多功能实体的形状和表面功能。 自组装将以两种方式使用： 1)以通过络合和轮烷形成产生嵌段和接枝类型的共聚物，以及在制备新型“滑动连接”大分子中使用与环状和线性组分相关的物理官能度，所述新型“滑动连接”大分子预期在拉伸和压缩中都是独特柔顺的。 这项研究的结果将涵盖从基本理解，实际应用到操纵已知骨架的性质以及制备全新类型的结构的范围。 ***

9320196 Gibson A "polyrotaxane" consists of cyclic molecules physically threaded onto a linear macromolecule with no covalent bonds between the cyclics and the linear backbone; bulky end groups may be fitted to the chain ends to prevent loss of the macrocycles via dethreading. Polyrotaxanes show unique behavior in terms of solubility, solid state structure and phase transitions. In this research, fundamental understanding of the threading of cyclic molecules by linear species is sought with respect to factors such as the nature of the two components (size, rigidity, structural similarity), the solvent (conformational aspects of the two components) and temperature. Entirely new polyrotaxanes of several types will be synthesized. Rotaxanes derived from polymeric macrocycles, both backbone and pendant, will be utilized in blend compatibilization and viscosity enhancement. Dendrimers with rotaxane surfaces will allow tailoring of the shape and surface functionality of these versatile entities. Self-assembly will be utilized in two ways: 1) to generate copolymers of block and graft types through complexation and rotaxane formation and 2 use of the physical functionality associated with the cyclic and linear components in the preparation of novel "slip link" macromolecules, which are expected to be uniquely compliant in both tension and compression. Results from this research will span the range from basic understanding, practical application to manipulate properties of known backbones, and preparation of entirely new types of structures. ***