The iniferter technique in radical polymerization under UV and thermal conditions: a comparative study

Abstract

UV and thermal polymerisations of styrene were carried out in the presence of conventional ‘iniferters’. The mechanisms of the two methods were investigated and provided new insight into the livingness of the so-called iniferter technique. Chain extension polymerisations were performed using symmetrical iniferters to check the living character of this technique under UV and thermal polymerization conditions. In accordance with the work of Otsu, we have shown that polymerisation under UV irradiation initiated by iniferters proceeds via the classical iniferter living (controlled) mechanism. On the other hand, thermal polymerisations were predominantly controlled by the reversible additionfragmentation chain transfer (RAFT) mechanism.

Controlled radical polymerization by carboxyl‐ and hydroxyl‐terminated dithiocarbamates and xanthates

“…It is the opposite of the inhibition/retardation observed in some other RAFT processes, noticeably those mediated by certain dithiobenzoates 2. Figure 3 shows the evolution of conversion is close to linear after a fast start, suggesting that a constant radical concentration is maintained 24. Polydispersities of all polymer samples taken throughout the polymerizations are constant in the range of 1.9–2.0.…”

A library of thiol‐terminated methacrylate telomers prepared by photoinitiated iniferter mediated polymerization for use in modifications of chromatographic surfaces by the “grafting to” approach

“…The iniferter‐concept was introduced by Otsu et al12 in early 1980's, and iniferters have since then been used to achieve control in thermally13–15 as well as photoinitiated polymerization systems,14–16 for the synthesis of both linear and branched mono‐ and co‐polymers. In iniferter mediated polymerizations, the control originates from the iniferter used and its characteristics.…”