Amphiphilic poly(ether urethanes) carrying associative terpyridine side groups with controlled spacing

Amphiphilic poly(ether urethanes) carrying associative terpyridine side groups with controlled spacing
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带有间距可控的缔合三联吡啶侧基的两亲性聚(醚型聚氨酯)

DOI:
10.1039/d1py00121c
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发表时间:
2021
期刊:
影响因子:
4.6
通讯作者:
S. Seiffert
S. Seiffert
中科院分区:
化学2区
文献类型:
--
作者:
K. Breul;S. Seiffert

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瞬时交联聚合物凝胶的合理设计需要深刻理解分子和拓扑因素如何决定材料的机械和动态性能。为了完善迄今为止建立的结构-性质关系,互补且通用的模型系统仍然是至关重要的先决条件。在本研究中,描述了金属超分子缔合三联吡啶二醇(称为贴纸)的合成及其与严格交替与随机序列和可变贴纸间距的聚乙二醇(pEG)基聚氨酯(PU)的结合。随机 PU 中多个相邻聚氨酯和贴纸单元的接近所产生的协同效应反映在熔融状态下的氢键特性及其溶液行为中。虽然交替的 PU 在水中形成胶束聚集体,其大小很大程度上取决于浓度和温度,从而导致 pEG 长度依赖的热响应性,但随机 PU 是水不溶性的。最后,对锰 (II) 交联 PU 凝胶进行的剪切流变测量表明,在随机 PU 的情况下,网络弛豫时间严重延长,并且终端流动状态中幂律尺度的加剧变浅。
The rational design of transiently crosslinked polymer gels requires a profound understanding of how molecular and topological factors determine the mechanical and dynamic material properties. To refine so-far established structure–property relations, complementary and versatile model sytems are still a crucial prerequisiste. In this study, the synthesis of a metallo-supramolecular associating terpyridine-diol (referred to as sticker) and its incorporation into poly(ethylene glycol) (pEG) based polyurethanes (PU) with strictly alternating vs. random sequences and variable sticker spacings is described. Synergetic effects resulting from the proximity of multiple neighboring urethane and sticker units in the random PUs are reflected in the hydrogen-bonding characteristics in the melt state as well as in their solution behavior. While the alternating PUs form micellar aggregates in water, whose size strongly depends on concentration and temperature leading to a pEG-length-dependent thermo-responsiveness, the random PUs are water insoluble. Finally, shear rheological measurements performed on manganese(II)-crosslinked PU gels demonstrate severely prolonged network relaxation times and an exacerbated shallowing of the power-lawscaling in the terminal flow regime in case of the random PUs.
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