On the Polymerization Behavior of Telomers: Metathesis versus Thiol−Ene Chemistry

Abstract

The potential of butadiene ditelomers for the synthesis of polymers has been investigated for the first time following two different approaches: acyclic diene metathesis (ADMET) polymerization and thiol−ene polyaddition. The feasibility of both step-growth polymerization methods has been investigated by focusing on the particular polymerization behavior of these unusual monomers. It has been shown that ring-closing metathesis of the studied ditelomers predominates in the first steps of ADMET, followed by oligomerization and double bond isomerization. On the other hand, during thiol−ene polyaddition, additional isomerization reactions, converting allyl ether moieties to vinyl ether moieties, were observed. Generally, the thiol−ene polymerization approach led to higher molecular weight polymers with better characteristics and interesting material properties.