During the last 20 years, controlled radical polymerization (CRP) has revolutionized the way polymer architectures can be designed. The myriad of monomers that can be polymerized with CRP allows combining in a large numbers of structures polymers with antagonistic, complementary or cooperative properties. Despite its industrial importance, ethylene remained for a very long time one of the last monomers which remained not controlled by radical polymerization. Recently, C2P2 showed that CRPs based on a reversible degenerative chain transfer, such as RAFT and TERP technologies, were excellent tools to control the radical polymerization of ethylene under mild conditions (≤ 200 bar, ≤ 80°C). However, whereas these systems allowed to synthesize chain-growth controlled PE, they both suffered from a distinct side reaction. Another well-established RDRP technique is the iodine-transfer polymerization (ITP) discovered in the 80s that was essentially applied to fluorinated monomers and as far as we know not to ethylene. Different iodo-chain-transfer agents (CTAs), commercially available, cheap, and non-toxic were used to investigate the impact of the R-group on the ITP of ethylene. These systems showed no rate retardation. Iodo chain ends were retained during polymerization and the iodo-polyethylene (PE–I) species was very stable upon storage. Narrow molar-mass distributions with dispersities, around 1.6 were obtained and number average molar masses, Mn, of 5000 g mol-1. The copolymerization with a polar monomer, vinyl acetate, was also discussed together with the use of more complex CTAs allowing the formation of more complex and well-defined macromolecular architectures based on PE.

Iodine-transfer polymerization of ethylene

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.