遥爪polymer熔体晶格模型中的自组装和玻璃形成：粘性键刚度的影响
Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds
摘要：
强相互作用，自组装遥爪聚合物的晶格集团理论（LCT）提供了一个理论工具，使建立自组装聚合物的重要微观分子细节和它们的本体热力学之间的联系。用于遥爪聚合物的自组装的原始LCT考虑完全柔性线性链的模型[J. Dudowicz和K. F. Freed，J. Chem. Phys. \textbf{136}，064902（2012）]，而我们最近的工作通过包括对每个单独的遥爪链内的键的链半柔性的描述而引入了对LCT的显著改进[W. S. Xu和K. F. Freed，J. Chem. Phys. \textbf{143}，024901（2015）]，但遥爪末端之间的物理缔合（或称为“粘性”）键保持为完全柔性。受普遍存在的空间位阻约束赋予额外程度的键刚度（或刚性）的真实遥爪聚合物的关联的启发，本文进一步扩展了LCT，以允许粘性键是半柔性的，但具有不同于每个遥爪链内的刚度。线性遥爪聚合物熔体的Helmholtz自由能的解析表达式提供了这个模型，并说明性的计算证明了显着的影响力的自组装和热力学遥爪聚合物的粘性债券的刚度。还提供了一个简短的讨论的影响，自组装玻璃形成相结合的LCT描述这种扩展模型的遥爪聚合物的结构弛豫时间和构型熵之间的亚当-吉布斯关系。
英文摘要：
The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. \textbf{136}, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telecheic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. \textbf{143}, 024901 (2015)], but the physically associative (or called "sticky") bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with the Adam-Gibbs relation between the structural relaxation time and the configurational entropy.
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