Abstract

‘Living’ ring-opening metathesis polymerization (ROMP) permits the synthesis of narrow-distribution homopolymers and well-defined block copolymers – provided no side reactions occur. However, acyclic metathesis between the chain end and double bonds in the polymer backbone competes with propagation during ROMP of cyclopentene, even with a mild Mo catalyst, though the rate constant is some 1600-fold smaller. ‘Dead’ chains in the reaction mixture can also be attacked; the products of acyclic metathesis are tagged by quenching the ROMP reaction with pyrenecarboxaldehyde. The extent of acyclic metathesis can be minimized through proper choice of reaction conditions, permitting the synthesis of narrow-distribution polycyclopentene with 100 kg/mol molecular weight.

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