Influence of residual impurities on ring-opening metathesis polymerization after copper(I)-catalyzed alkyne-azide cycloaddition click reaction

Jinwoong Choi, Hyunjoo Kim, Taeyang Do, Junsoo Moon, Youngson Choe, Jeung Gon Kim, Joona Bang

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

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.

Original languageEnglish
JournalJournal of Polymer Science, Part A: Polymer Chemistry
DOIs
Publication statusAccepted/In press - 2019 Jan 1

Fingerprint

Alkynes
Azides
Cycloaddition
Ring opening polymerization
Copper
Impurities
Polymers
Catalysts
Poisons
Molecular weight distribution
Free radical polymerization
Molecular weight
Ligands
Polymerization

Keywords

  • copper(I)-catalyzed alkyne-azide cycloaddition reaction
  • living polymerization
  • macromonomers
  • ROMP

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Influence of residual impurities on ring-opening metathesis polymerization after copper(I)-catalyzed alkyne-azide cycloaddition click reaction. / Choi, Jinwoong; Kim, Hyunjoo; Do, Taeyang; Moon, Junsoo; Choe, Youngson; Kim, Jeung Gon; Bang, Joona.

In: Journal of Polymer Science, Part A: Polymer Chemistry, 01.01.2019.

Research output: Contribution to journalArticle

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