Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

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• 作者：Suk-kyun Ahn ; Deanna L. Pickel ; W. Michael Kochemba ; Jihua Chen ; David Uhrig ; Juan Pablo Hinestrosa ; Jan-Michael Carrillo ; Ming Shao ; Changwoo Do ; Jamie M. Messman ; W. Michael Brown ; Bobby G. Sumpter ; S. Michael Kilbey ; II
• 刊名：ACS Macro Letters
• 出版年：2013
• 出版时间：August 20, 2013
• 年：2013
• 卷：2
• 期：8
• 页码：761-765
• 全文大小：279K
• 年卷期：v.2,no.8(August 20, 2013)
• ISSN：2161-1653

文摘

We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of 蟺鈥撓€ interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.