Synthesis and Properties of Novel Polymers with Rotaxane Architectures

9320196 Gibson“聚轮烷”由环分子物理地连接到线性大分子上，环分子与线性主链之间没有共价键；大的端群可以安装到链端，以防止通过脱线丢失大环。聚轮烷在溶解度、固相结构和相变方面表现出独特的性能。在这项研究中，我们从两个组分的性质（大小、刚性、结构相似性）、溶剂（两个组分的构象方面）和温度等因素出发，寻求对环状分子的线状物种穿线的基本理解。将合成几种类型的全新聚轮烷。由聚合物大环衍生的轮烷，包括主链环和链链环，将用于共混增容和增粘。具有轮烷表面的树状大分子将允许剪裁这些多功能实体的形状和表面功能。自组装将以两种方式利用：1)通过络合和轮烷形成生成嵌段和接枝类型的共聚物；2使用与环状和线性组分相关的物理功能来制备新型“滑移连接”大分子，这些大分子有望在张力和压缩中都具有独特的柔顺性。这项研究的结果将跨越从基本理解，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. ***