Bottlebrush polymers (BBPs) are three-dimensional polymers with great academic and industrial potential owing to their highly tunable and intricate architecture. The most popular method to synthesize BBPs is ring-opening metathesis polymerization (ROMP) with Grubbs' catalyst, allowing living grafting-through polymerization of macromonomers of up to ultrahigh molecular weights with narrow molecular weight distribution. In this case, it has been well recognized that the purity of macromonomers (MMs) is critical for a successful ROMP reaction. For MMs synthesized from reversible-deactivation radical polymerization, Grubbs and Xia demonstrated that the better control of ROMP reaction can be achieved when they are prepared via “growth-then-coupling” method that is coupling a norbornenyl group to end-functionalized prepolymers. However, these MMs can also contain various residual impurities from previous synthetic steps, which can potentially poison the catalyst and hamper the ROMP reaction. Herein, we intentionally doped possible impurities into purified MMs to identify the most poisoning species. As a result, it was found that alkyne-functionalized norbornene most significantly retarded the ROMP reaction due to a formation of Ru-vinyl-carbene intermediates having low catalytic reactivity, whereas the other reagents such as solvent, Cu-catalyst, ligands, and azido-terminated prepolymers were relatively inert.
|Number of pages||12|
|Journal||Journal of Polymer Science, Part A: Polymer Chemistry|
|Publication status||Published - 2019 Mar 15|
Bibliographical noteFunding Information:
2018R1A2B2004508 and 2018M3D1A1058536) and also by the Global Frontier R&D Program (No. 2013M3A6B1078869) on Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, ICT and Future Planning.
This work was supported by the National Research Foundation of Korea grant funded by the Korean government (MSIP; Nos.
© 2019 Wiley Periodicals, Inc.
- copper(I)-catalyzed alkyne-azide cycloaddition reaction
- living polymerization
ASJC Scopus subject areas
- Polymers and Plastics
- Organic Chemistry
- Materials Chemistry