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Updated: Aug 21, 2025

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
Chain transfer agents for the catalytic ring opening metathesis polymerization of norbornenes
Indradip Mandal1, Ankita Mandal1, Md Atiur Rahman1
1Department of Chemistry, University of Fribourg Chemin du Musée 9 1700 Fribourg Switzerland andreas.kilbinger@unifr.ch.
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 via 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.
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