Synthesis of fluoroalkyl end-capped oligomers with fluoroalkanoyl peroxides-architecture of self-assembled aggregates of these oligomers

Citation
H. Sawada et T. Kawase, Synthesis of fluoroalkyl end-capped oligomers with fluoroalkanoyl peroxides-architecture of self-assembled aggregates of these oligomers, KOBUNSH RON, 58(4), 2001, pp. 147-160
Citations number
59
Language
GIAPPONESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
KOBUNSHI RONBUNSHU
ISSN journal
0386-2186 → ACNP
Volume
58
Issue
4
Year of publication
2001
Pages
147 - 160
Database
ISI
SICI code
0386-2186(2001)58:4<147:SOFEOW>2.0.ZU;2-Y
Abstract
Fluoroalkanoyl peroxides were demonstrated to exhibit quite different decom position behavior from the corresponding nonfluorinated alkanoyl peroxides, owing to the strong electron-withdrawing properties of the fluoroalkyl gro ups. In fact, fluoroalkanoyl peroxides decompose easily to afford fluoroalk yl radicals with a concerted homolytic dissociation with a three-bond fissi on. This unique behavior was applied to the direct introduction of the fluo roalkyl group into the end-sites of oligomeric molecules via a radical proc ess. These fluoroalkyl end-capped oligomers thus obtained possess good solu bility not only in water but also in common organic solvents. Additionally, these fluoroalkyl end-capped oligomers were able to reduce the surface ten sion of watts and organic solvents veri effectively with a clear break poin t resembling a CMC (critical micelle concentration). This finding and stati c light scattering measurements showed that these fluoroalkyl end-capped ol igomer can form the self-assembled molecular aggregates with the aggregatio ns of end-capped fluoroalkyl segments in these solvents. In particular inte rest, fluoroalkyl end-capped oligomers containing betaine segments or hydro xyl segments could cause gelation derived from the synergistical interactio n of the aggregations of end-capped fluoroalkyl segments and the ionic inte ractions of betaine segments (or the intermolecular hydrogen-bonding intera ctions between hydroxyl segments) in water and polar organic solvents.