Abstract
This paper presents a new approach toward the introduction of both short- (SCB) and long-chain branching (LCB) in polyethylene-like polyesters via the ring-opening polymerization of macrolactones. Macrolactones containing an alkyl (S1) or alcohol (S2) branch were obtained using radical thiol–ene chemistry of ambrettolide (Amb). Kinetic studies revealed the need for an excess of thiol to achieve a high conversion of the double bond. Even though homopolymerization of the three monomers Amb, S1, and S2 revealed comparable reactivities, the molecular weight buildup during polymerization of S2 differs drastically from that of Amb and S1. Instead of the linear increase of Mn with conversion observed for Amb and S1, the molecular weight buildup for the ring-opening polymerization of S2 resembles that of a step-growth polymerization—slow buildup at low and moderate conversion followed by a rapid increase in molecular weight at high conversions. This disparity was attributed to the possibility of S2 to function as...
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