Biomimetic Processes. IV. Carbocationic Polymerization of Isoprene Initiated by Dimethyl Allyl Alcohol

Judit E. Puskas (1) , Clément Peres (2) , Frédéric Peruch (2, 3) , Alain Deffieux (2, 3) , David E. Dabney (4) , Chrys Wesdemiotis (4) , Serap Hayat-Soytas (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

In this article, we investigate a new bio-inspired synthetic route towards NR homologs based on the carbocationic polymerization of isoprene initiated by dimethyl allyl alcohol (DMAOH)/TiCl4 or BF3 center dot Et2O as the catalytic system. This study is the continuation of our studies related to the proof of principle that NR biosynthesis is based on a carbocationic mechanism. It is shown that using the biomimetic strategy of initiation by allylic carbocations, polyisoprene carrying a dimethyl allyl head group is produced almost exclusively via 1,4 addition, yielding repeating units with cis and trans configurations

Mots clés: biomimetic; biosynthesis; cationic polymerization; natural rubber; polyisoprene; real-time FTIR

Domaines: Polymères

Judit E. Puskas, Clément Peres, Frédéric Peruch, Alain Deffieux, David E. Dabney, et al.. Biomimetic Processes. IV. Carbocationic Polymerization of Isoprene Initiated by Dimethyl Allyl Alcohol. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47 (8), pp.2181-2189. ⟨10.1002/pola.23293⟩. ⟨hal-00397638⟩