Study on the Entanglement Effect between Topologically Different Polymer Chains

为了理解缠结控制缩聚物体系物理性质的本质，我们研究了1）不同分子量的单分散聚苯乙烯的二元共混物，2）分散在聚丁二烯基体中的苯乙烯-丁二烯嵌段聚合物胶束，3）线性/4-臂星星聚苯乙烯的共混物，和4）具有截留的顺式聚异戊二烯的天然橡胶网络的松弛行为，使用粘弹性和介电光谱学。利用组分之一，例如1）高分子量组分。3)以星形链为探针，以自由链为探针，测定了探针的弛豫时间及其分布随体系分子量和组成的变化，可实现的弛豫模式取决于探针特征时间的相对长度和限制探针的基质链的相对长度。因此，我们可以分别评估探针的基本弛豫过程：根据“管”理论，它们是repatation，管更新和路径呼吸模式。在通常的本体聚合物体系中，这些模式以竞争的方式同时发生，因此不可分离。然而，通过利用探针组件的本方法，我们可以单独地在分子方面的系统中所涉及的弛豫过程进行评估和分析。从而阐明了凝聚体系中纠缠对柔性高分子链动力学的影响特征。在工业应用中，这些知识将为高抗冲塑料等最终产品的加工条件和性能设计提供重要线索。

To understand the nature of entanglement governing physical properties of condensed polymer systems, we examined the relaxation behavior of 1) binary blends of monodisperse polystyrenes of different molecular weight, 2) styrene-butadiene block polymer micelles dispersed in polybutadiene matrix, 3) blends of linear/4-arm star polystyrenes, and 4) natural rubber networks with entrapped cis-polyisoprene, employing viscoelastic and dielectric spectroscopy. Utilizing one of the components such as, for example, 1) the high molecular weight component. 3) the star-chains, and 4) the entrapped free chains as a probe, we determined the relaxation time and its distribution of the probes as a function of molecular weight and composition of the systems.Realizable relaxation modes are determined by relative length of the characteristic times of the probes and matrix chains confining the probes. Thus, we could separately evaluate the elementary relaxation processes of the probes: In terms of the "tube" theory, they are repatation, tube renewal, and path breathing modes. In usual bulk polymer systems, these modes take place si-multeneously in a competitice manner and thus unseparable. However, by the present methods utilizing a probe component, we could separately evaluate and interprete in molecular terms the relaxation processes involved in the systems. Thus, we could clarify the features of the effect of entanglement on the dynamics of flexible polymer chains in the condensed systems. In industrial application, these knowledges will provide important clues to design processing conditions and properties of end-products such as high-impact plastics.