Preparation of bis‐epoxy end capped macromonomers through anionic or RAFT polymerization.

The focus of this paper is to report the quantitative synthesis of bis‐epoxy end functionalized polyisoprene (BETPI) macromonomers by anionic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. For anionic polymerization, more stable and sterically hindered living anions polyisoprene (Li+‐PIp‐Li+) react with epichlorohydrin (ECH) for the synthesis of well‐defined BETPI. For the high‐pressure RAFT polymerization, a novel bis‐epoxy end functionalized trithiocarbonate (BODAAT) is designed as RAFT agent for the polymerization of isoprene monomer to obtain well‐defined BETPI. The functionalities of the resulting BETPI are analyzed by Fourier transform infrared spectroscopy (FT‐IR), NMR, and size exclusion chromatography (SEC). Through two polymerization methods, the BETPI with 600–1000 Da of molecular weight and over 75% of epoxy end capping rate is obtained, which can be further utilized as highly reactive liquid macromonomers. [ABSTRACT FROM AUTHOR]