Olefin metathesis catalysts are well-known for their versatility of catalyzing different mechanisms including ring-opening metathesis, ring-closing metathesis, and cross-metathesis. The combination of different olefin metathesis reactions in a same polymerization affords the construction of complex but well-defined chain topologies and thus becomes an intriguing topic.<br/>However, the mechanistic differences between olefin metathesis reactions can bring mutual influence between different mechanisms and the influence could be hardly described. The understanding of the mutual influence between different olefin metathesis mechanisms is therefore crucial for the design of olefin metathesis polymerization with different mechanisms. In the present work, we utilize the theory of binary polymerization to assess the mutual influence between olefin metathesis mechanisms. The mutual influence can be characterized quantitatively via kinetic simulations. The relationship between the mutual influence of different olefin metathesis mechanisms and the effect of various parameters such as structure of the monomer, solvent, concentrations, etc. are carefully studied and used for the construction of polymers with various topologies including linear polymer, ring polymer, hyperbranched polymer, and bottlebrush polymer. This work demonstrates how to study the mutual influence between different polymerization mechanisms using the theory of binary polymerization and reveals the potential of combining different mechanisms with mutual influence in a same polymerization reaction.

Hybrid olefin metathesis polymerization

ACS Spring 2022

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