Catalytic Living Ring Opening Metathesis Polymerisation: The Importance of Ring Strain in Chain Transfer Agents. (11th September 2019)

• Record Type: Journal Article
• Authors: Liu, Peng; Yasir, Mohammad; Kilbinger, Andreas F. M.
• Is Part Of: Angewandte Chemie. Volume 131:Number 43(2019)
• Page Start: 15422
• Page End: 15426
• Publication Date: 2019-09-11
• Subjects: Kettentransferreagentien -- Lebende Polymerisation -- Olefinmetathese -- Ringöffnungspolymerisation -- Ringspannung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201907921
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A recently developed catalytic living ring opening metathesis polymerisation (ROMP) was investigated using a series of reversible chain transfer agents (CTA) carrying either cyclopentene or cyclohexene rings, differing only in ring strain. All cyclopentene derivatives examined showed significantly faster reaction rates than the corresponding cyclohexene derivatives. This resulted in lower molecular weight dispersities and better control of the molecular weight for the cyclopentene compared to the cyclohexene CTAs. Both Grubbs' second and third generation catalysts could be employed in catalytic living ROMP using cyclopentene CTA derivatives. The kinetics of different CTAs were studied, block copolymers were synthesised and residual ruthenium quantified by ICP‐OES. All polymers were fully characterised by NMR, GPC and MALDI‐ToF mass spectrometry. The new cyclopentene CTAs are readily synthesised in a few straightforward steps and provide faster reaction kinetics than all previously reported reversible CTAs. Abstract : Eine Serie von reversiblen Kettenübertragungsreagentien mit entweder Cyclopenten‐ oder Cyclohexenringen wurde in der katalytischen Metathesepolymerisation (ROMP) eingesetzt. Die Cyclopentenderivate zeigen deutlich höhere Reaktionsgeschwindigkeiten als die entsprechenden Cyclohexenderivate und ermöglichen niedrigere Molekulargewichtsdispersionen und eine bessere Kontrolle des Molekulargewichts.