Ceric ion-reducing agent redox initiated vinyl polymerisation

Subramanian, S. V. ; Santappa, M. (1968) Ceric ion-reducing agent redox initiated vinyl polymerisation Die Makromolekulare Chemie, 112 (1). pp. 1-15. ISSN 0025-116X

Full text not available from this repository.

Official URL: http://onlinelibrary.wiley.com/doi/10.1002/macp.19...

Related URL: http://dx.doi.org/10.1002/macp.1968.021120101


Ceric perchlorate/formaldehyde (F)redox couple initiated polymerisation of the monomer methyl acrylate (MA), acrylonitrile (AN), and methyl methacrylate (MMA) in perchloric acid (25°C) was carried out. The rate of polymerisation was directly proportional to [M]2 and [F] for all the systems. The rate was independent of [Ce4+] for the systems with MA or AN, but inversely proportional to [Ce4+] with MMA as the monomer. The rate of ceric disappearance was directly proportional to [Ce4+], [F], and [M]. The results were explained by a kinetic scheme involving the oxidation of the substrate by Ce4+ to give the primary radical and further reaction of the latter with Ce4+ to give the final product, and initiation of polymerisation both by Ce4+ and the primary radical, propagation followed by termination by the metal ion. Only with MMA as the monomer, the initiation by Ce4+ was found to be negligible compared to that by primary radicals. In the system with the reducing agents t-butanol and n-butanol, there was found to be 1:1 complex formation between the substrate and Ce4+. Otherwise the scheme is similar to that proposed for the Ce4+/HCHO/HClO4/AN (MA) systems.

Item Type:Article
Source:Copyright of this article belongs to Huthig & Wepf Verlag, Basel.
ID Code:43355
Deposited On:11 Jun 2011 08:44
Last Modified:11 Jun 2011 08:44

Repository Staff Only: item control page