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Advances in Controlled/Living Radical Polymerization by Krzysztof Matyjaszewski

By Krzysztof Matyjaszewski

Offers new advancements in controlled/living radical polymerization in 3 components: atom move radical polymerization (ATRP), nitroxide mediated polymerization (NMP), and reversible addition-fragmentation move (RAFT). additionally comprises synthesis and characterization of many new materials.

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2. Dithioester-Mediated (RAFT) Polymerization When a RAFT process is sufficiently fast with no side reaction accompanied, it provides an ideal DT process. 17). The bulk polymerization of styrene was carried out at 60°C with this DT (RAFT) agent and varying concentrations of BPO, confirming the first-order kinetics eq 3 to hold. The absolute value of R was approximately thes ame as in the absence of the RAFT agent. (Actually, it showed a weak dependence on the RAFT agent concentration: the larger was the RAFT agent concentration, the smaller was R .

The addition of 40mM of the conventional initiator VR110 to this system increased R b y a factor up to about 3, as shown by the squares in Figure 3a. Figure 3b shows the comparison of the PDI equations 2 and 4 (k = Aa[Cu(I)Br] ) with the experiments with [VR110] = 0 (circles) and [VR110]o = 40mM (square), respectively. In both systems, satisfactory agreement of theory and experiment was found. It was confirmed for the ATRP system, too, that conventional initiation not only increases the polymerization rate but lowers the polydispersity (at least at an initial stage of polymerization where the contribution of terminated chains to polydispersity is insignificant).

ACS Symposium Series; American Chemical Society: Washington, DC, 2003. ch004 56 Macroradicals with the radical site being located somewhere on the backbone should primarily occur at high degrees of monomer conversion and, within S P PLP experiments, at large observation times, where t exceeds the time interval estimated for the transfer-to-polymer reaction. A t lower conversions and at shorter observation times t, termination should proceed primarily via chain-end encounters. 16. 2 up to 15 or even 20 % monomer conversion, which is well above the range in which the polymer solution is considered to be dilute.

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