Engineering of Molecular Geometry in Bottlebrush Polymers
Engineering of Molecular Geometry in Bottlebrush Polymers
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DOI：
10.1021/acs.macromol.9b00845
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发表时间：
2019-06
期刊：
影响因子：
5.5
通讯作者：
D. Walsh;Sarit Dutta;C. Sing;Damien Guironnet
中科院分区：
文献类型：
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作者：
D. Walsh;Sarit Dutta;C. Sing;Damien Guironnet
瓶刷状聚合物是大的圆柱形大分子，其中分子“宽度”来自密集地附接到中心主链的大量侧链。这些接枝侧链的长度间接控制分子柔性、材料加工和分子组装行为。侧链长度的测序是进一步修饰分子几何形状的有前途的途径;然而，繁琐的实验室合成对这种可调性施加了实际限制。在这里，我们开发了一种方法来克服这一限制，利用自动化合成和计算机模拟工程瓶刷聚合物的三维分子几何形状。自动化流动合成平台结合了流体力学、反应器工程和活性聚合原理，可对聚合物结构进行精确的合成控制。具有沙漏形、足球形、蝴蝶结形和球形结构轮廓的瓶刷状聚合物是以高分子量（高达106.
Bottlebrush polymers are large cylindrical macromolecules, where a molecular “width” emerges from a large number of side chains densely attached to a central backbone. The lengths of these grafted side chains exert indirect control over molecular flexibility, material processing, and molecular assembly behavior. Sequencing of the side-chain length is a promising route to further modify molecular geometry; however, tedious laboratory synthesis has imposed practical limits on this tunability. Here, we develop a methodology to overcome this limitation, leveraging automated synthesis and computer simulations to engineer bottlebrush polymers with three-dimensional molecular geometries. The automated flow synthesis platform combines fluid mechanics, reactor engineering, and living polymerization principles to gain precise synthetic control over the polymer architecture. Bottlebrush polymers with hourglass, football, bowtie, and sphere architecture profiles are synthesized with high molecular weights (up to 106 ...