高分子凝胶的力学和物理化学性质研究

K. Urayama
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引用次数: 3

摘要

本文综述了本研究的三个方面:(1)末端连接聚合物网络橡胶弹性的分子理解和捕获客体链的动力学;(2)通过聚合物网络的拓扑控制,获得对频率和温度都不敏感的具有显著延展性或高阻尼的弹性体;(3)聚合物网络体系中的相变,如溶胶-凝胶相变和向列向-各向同性相变驱动的体积相变。基于端链聚二甲基硅氧烷(PDMS)网络的双轴延伸数据,评估了应变能密度函数的形式,明确了橡胶弹性的五种缠结模型。结果表明,交联网络中的线性客体链的动力学服从重复概念。在网目尺寸小于纠缠间距的主机网络中,观察到复制的显著减缓。在稀释状态下,通过末端连接长前驱体并去除溶剂制备的溶胀网络具有超过3000%的明显延展性以及非常弱的应力应变依赖性。这些特征源于少量的被困缠结和紧凑的网络链构象。含有多垂链的不规则网络的阻尼随垂链数量的增加而增加。由于不规则网络结构的缓慢粘弹性松弛,阻尼对温度和频率的依赖性非常弱。在向列或各向同性溶剂中膨胀的向列网络经历了膨胀的各向同性和收缩的向列状态之间的相变。
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Studies on mechanical and physicochemical properties of polymer gels
The three topics in our study are reviewed in the present paper: (1) molecular understandings of rubber elasticity of end-linked polymer networks and the dynamics of trapped guest chains; (2) elastomers with remarkable extensibility or high damping insensitive to both frequency and temperature via topology control of polymer networks; (3) phase transition in polymer network systems such as sol-gel transition and volume phase transition driven by nematic-isotroptic transition. On the basis of the biaxial elongation data of end-linked polydimethylsiloxane (PDMS) networks, the form of the strain energy density function is evaluated, and the five entanglement models of rubber elasticity are unambiguously assessed. It is shown that the dynamics of linear guest chains trapped in crosslinked networks obey the reptation concept. A dramatic slowing down of the reptation is observed in the host network whose mesh size is smaller than the entanglement spacing. The deswollen networks, prepared by end-linking long precursors in the diluted state and removing the solvent, exhibit a marked extensibility over 3000% as well as a very weak strain dependence of stress. These features stem from a small amount of trapped entanglement and a compact conformation of network chains. The damping of irregular networks containing many pendant chains increases with the amount of pendant chains. The damping is very weak dependent of temperature and frequency as a result of a slow viscoelastic relaxation of irregular network structures. The nematic networks swollen in nematic or isotropic solvents undergo a phase transition between the swollen isotropic and shrunken nematic states.
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