One-Step Ring Opening Metathesis Block-Like Copolymers and their Compositional Analysis by a Novel Retardation Technique

Mohammad Yasir, Peng Liu, Jens C. Markwart, Oksana Suraeva, Frederik R. Wurm, Jansie Smart, Marco Lattuada, Andreas F.M. Kilbinger*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Using a one-step synthetic route for block copolymers avoids the repeated addition of monomers to the polymerization mixture, which can easily lead to contamination and, therefore, to the unwanted termination of chain growth. For this purpose, monomers (M1–M5) with different steric hindrances and different propagation rates are explored. Copolymerization of M1 (propagating rapidly) with M2 (propagating slowly), M1 with M3 (propagating extremely slowly) and M4 (propagating rapidly) with M5 (propagating slowly) yielded diblock-like copolymers using Grubbs’ first (G1) or third generation catalyst (G3). The monomer consumption was followed by 1H NMR spectroscopy, which revealed vastly different reactivity ratios for M1 and M2. In the case of M1 and M3, we observed the highest difference in reactivity ratios (r1=324 and r2=0.003) ever reported for a copolymerization method. A triblock-like copolymer was also synthesized using G3 by first allowing the consumption of the mixture of M1 and M2 and then adding M1 again. In addition, in order to measure the fast reaction rates of the G3 catalyst with M1, we report a novel retardation technique based on an unusual reversible G3 Fischer-carbene to G3 benzylidene/alkylidene transformation.

Original languageEnglish
Pages (from-to)13597-13601
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number32
DOIs
Publication statusPublished - 3 Aug 2020
Externally publishedYes

Keywords

  • block copolymers
  • olefin metathesis
  • ring opening metathesis polymerization

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