Catalytic living ROMP: block copolymers from macro-chain transfer agents.

Vinyl ether based macro-chain transfer agents (m-CTAs) are used to produce different di or tri-block copolymers under catalytic living ROMP conditions. Polystyrene (PS) vinyl ether m-CTA and polycaprolactone (PCL) or polylactide vinyl ether (PLA) m-CTAs are synthesized straightforwardly ATRP and ROP respectively. Regioselectivity as well as the high metathesis activity of these m-CTAs enabled us to synthesise a range of metathesis-based A-B diblock copolymers with controlled dispersities ( < 1.

Chain transfer agents for the catalytic ring opening metathesis polymerization of norbornenes.

Here, we present a detailed study of the metathesis activity of conjugated 1,3 diene derivatives in ring opening metathesis polymerization (ROMP) using Grubbs' 3rd generation catalyst (G3). A comprehensive screening of those derivatives revealed that monosubstituted 1,3 dienes show similar reactivities towards G3-alkylidenes as norbornene derivatives. Therefore, they represent perfect candidates for chain transfer agents in a kinetically controlled catalytic ROMP.

Oxanorbornenes: promising new single addition monomers for the metathesis polymerization.

Higher ring-opening metathesis propagation rates of -norbornene derivatives over derivatives are well established in the literature. Here, we report for the first time that -isomers of oxanorbornene derivatives show higher reactivity towards ring-opening metathesis with Grubbs' 3rd generation catalyst () than the corresponding -isomers. A very high selectivity for the reaction of with over the -isomers could be shown.