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Updated: May 14, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
A different route to functional polyolefins: olefin-carbene copolymerisation
Nicole M G Franssen1, Joost N H Reek, Bas de Bruin
1Van't Hoff Institute for Molecular Sciences (HIMS), Department of Homogeneous and Supramolecular Catalysis, Universiteit van Amsterdam, P.O. Box 94720, 1090 GS Amsterdam, The Netherlands.
This study introduces a new method for creating functional polymers by copolymerizing olefins and carbenes using Rh(I) catalysts. This technique offers a promising alternative to traditional polymerization, yielding highly functionalized copolymers with potential for diverse applications.
Area of Science:
- Polymer Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Traditional olefin polymerization methods have limitations in producing highly functionalized polymers.
- Developing controlled synthesis routes for functional polymers is crucial for advanced material applications.
Purpose of the Study:
- To investigate the copolymerization of olefins (ethene) and carbenes using Rh-based catalysts.
- To establish a proof-of-concept for a new methodology in controlled functional polymer synthesis.
Main Methods:
- Utilized Rh(I)(cod) catalyst precursors for olefin-carbene copolymerization.
- Analyzed polymer products using Maldi-ToF to confirm copolymer formation and composition.
- Investigated the effect of ethene pressure on copolymer composition and product distribution.
Main Results:
- Rh(I)(cod) catalysts successfully mediated the synthesis of high molecular-weight, highly functionalized copolymers.
- Copolymerization yielded a mixture of copolymers and carbene homopolymers, with ethene content up to 70% in specific fractions.
- Higher ethene pressures unexpectedly decreased average ethene content due to a shift towards homopolymer formation.
Conclusions:
- Olefin-carbene copolymerization mediated by Rh(I) catalysts presents a viable route for controlled synthesis of functional polymers.
- The catalyst system and reaction conditions significantly influence the copolymer composition and the ratio of copolymer to homopolymer.
- The resulting copolymers possess a blocky microstructure with stereoregular functional blocks and branching.
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