Biomimetic Carbocationic Polymerizations III: Investigation of Isoprene Polymerization Initiated by Dimethyl Allyl Bromide

Judit E. Puskas (1) , Frédéric Peruch (2, 3) , Alain Deffieux (2, 3) , David E. Dabney (4) , Chrys Wesdemiotis (4) , Hai Bo Li (1) , Allia Lindsay (5)

1 Univ Akron, Dept Polymer Sci
2 LCPO - Laboratoire de Chimie des Polymères Organiques
3 Team 1 LCPO : Polymerization Catalyses & Engineering
4 Department of Chemistry [Akron]
5 Agnes Scott Coll, Decatur, GA

Natural rubber (poly(1,4-cis-isoprene), NR) is a polymer of considerable industrial importance due to its exceptional properties. It is mostly produced from the cultivation of Hevea brasiliensis, and to a limited extent from Parthenium argentatum. Till date none of the synthetic equivalent of NR exists. Recently we suggested that the mechanism of NR biosynthesis is based on carbocationic polymerization, similarly to that of natural oligoisoprenoids forming by enzyme-catalyzed prenylation. In this article we present proof of concept of a new bio-inspired synthetic route towards the synthesis of polyisoprenes based on carbocationic polymerization initiated by dimethyl allyl bromide (DMABr)/TiCl4. It is shown that using this strategy, 1,4-oligoisoprene carrying a dimethyl allyl head group is produced in both cis and trans configurations, together with cyclized sequences

Mots clés: biomimetic; biomimetic processes; carbocationic polymerization; cationic polymerization; FT-IR; natural rubber; polyisoprene; real-time FTIR

Domaines: Polymères

Judit E. Puskas, Frédéric Peruch, Alain Deffieux, David E. Dabney, Chrys Wesdemiotis, et al.. Biomimetic Carbocationic Polymerizations III: Investigation of Isoprene Polymerization Initiated by Dimethyl Allyl Bromide. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47 (8), pp.2172-2180. ⟨10.1002/pola.23294⟩. ⟨hal-00397630⟩