Connectivity defects enhance chain dynamics in supramolecular polymer model‐network gels

Connectivity defects enhance chain dynamics in supramolecular polymer model‐network gels
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连接缺陷增强了超分子聚合物模型网络凝胶中的链动力学

DOI:
10.1002/polb.24250
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发表时间:
2016
期刊:
Journal of Polymer Science Part B
影响因子:
--
通讯作者:
S. Seiffert
S. Seiffert
中科院分区:
--
文献类型:
--
作者:
A. Habicht;S. Czarnecki;T. Rossow;S. Seiffert

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超分子聚合物网络表现出双重动力学:它们的聚合物链和它们之间的瞬时键,当不规则的网络结构导致两者的局部变化时,这进一步复杂化。典型的不规则性是不完美的网络链连接。为了评估其影响,我们研究了三种不同类型的示踪聚合物在四臂星星形聚乙二醇超分子模型网络中的扩散。首先,我们专注于示踪剂,携带三个贴纸和一个荧光标记在他们的四个手臂,从而在他们附近创建一个固有的网络连接缺陷。第二,我们嵌入了带有四个标签和四个标签的示踪剂,并且这些示踪剂本身不会产生网络缺陷。第三,我们嵌入了比网络网格更大的非粘性示踪剂,从而在空间上阻碍了它们的连接。这些研究表明,第一示踪剂可以通过c * 以上的连续臂分离在网络内快速行走,而c * 以下,它们受到释放和凝胶簇结合部分的动态平衡。相比之下,第二示踪剂被有效地纳入网络,这极大地阻碍了它们的运动。与此相反,第三种示踪剂几乎可以不受阻碍地扩散,就好像它们嵌入未交联的基质中一样。© 2016 Wiley Periodicals,Inc. J.波利姆科学,部分B:聚合物物理2017,55,19-29
Supramolecular polymer networks exhibit twofold dynamics: that of their polymer chains and that of the transient bonds between them, which is further complexed when irregular network structures lead to local variation of both. A typical irregularity is imperfect network‐chain connectivity. To assess the impact of that, we study the diffusion of three different types of tracer polymers in supramolecular model networks of four‐arm star‐shaped poly(ethylene glycol). First, we focus on tracers that carry three stickers and one fluorescent label at their four arms, thereby creating an inherent network connectivity defect in their vicinity. Second, we embed tracers that carry four stickers and four labels and that donotintrinsically create network defects. Third, we embed non‐sticky tracers with a larger size than the network meshes, thereby sterically obstructing their connectivity. These studies reveal that the first tracers can rapidly walk within the networks by sequential arm detachment abovec*, whereas belowc*, they are subject to a dynamic equilibrium of liberated and gel‐cluster‐bound portions. By contrast, the second tracers are efficiently incorporated into the network, which dramatically hinders their motion. Opposed to that, the third tracers can diffuse almost as unhindered as if they were embedded within an uncrosslinked matrix. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2017,55, 19–29
DOI: 10.1021/ma401111n
发表时间: 2013-09-24
期刊: MACROMOLECULES
影响因子: 5.5
作者:
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