Atom transfer radical polymerization of styrene initiated by polychloroalkanes and catalyzed by CuCl/2,2′-bipyridine: A kinetic and mechanistic study

✍ Scribed by Mathias Destarac; Jean-Marie Bessiere; Bernard Boutevin

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 281 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19981130)36:16<2933::aid-pola12>3.0.co;2-w

✦ Synopsis

A series of polychloroalkanes, known as telogen agents for redox telomerization, were used as initiators for atom transfer radical polymerization (ATRP) of styrene using the heterogeneous CuCl/2,2Ј-bipyridine catalyst. In copper-catalyzed redox telomerization, the reactivity of RCCl 3 -type telogens is strongly influenced by the nature of the R group. In ATRP, the 2,2Ј-bipyridine ligand levels the activity of the catalytic system in such a way that all 1,1,1-trichloroalkanes are efficient initiators in ATRP, whatever the R group. The nature of this substituent influences the overall rate of polymerization through both the number of active sites per chain and the [Cu (I)]/[Cu (II)] ratio. By the combining of several analytical techniques, it is proved that some polychloroalkanes such as CCl 3 CO 2 CH 3 , CCl 3 CF 3 , or CCl 4 are bifunctional initiators. Finally, a general mechanism of initiation is proposed.