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

Abstract

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. This unprecedented reactivity allowed us to catalytically synthesize mono-end-functional poly(norborneneimide)s on the gram scale. Much more complex architectures such as star-shaped polymers could also be synthesized catalytically for the very first time <i>via</i> ROMP. This inexpensive and greener route to produce telechelic ROMP polymers was further utilized to synthesize ROMP block copolymers using bifunctional ROMP and ATRP/NCL initiators. Finally, the regioselective reaction of G3 with 1,3 diene derivatives was also exploited in the synthesis of a ROMP-PEG diblock copolymer initiated from a PEG macroinitiator.