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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Russell, G . ; van Herk, A . M. Macromol. Chem. Phys. 1997, 198, 1545. Listigover, Ν . ; Georges, M . K . ; Odell, P. G . ; Keoshkerian, B . Macromolecules 1996, 29, 8992. ; Fischer, H . Macromolecules 2000, 33, 4403. ; Fischer, H . J. Amer. Chem. Soc. 2001, 123, 2849, and references therein. This was not recognized in our earlier work11b inspite of a thoughtful remark of a referee. D . Bertin, O. Guerret, private communication. ; Fukuda, T. Macromolecules 2003, 36, 908. ; Matyjaszewski, K . Maromol.

For more general equations of rate and PDI, see refs (7). For LRP with an A T process (ATRP), all the above equations are valid by the reinterpretations of k = k [A],k = k^, and X* = A X . In LRP with a DT process, radicals must be generated by a conventional initiation to start and maintain polymerization. If the DT process is not a retarding or degrading one, or accompanies no side reaction, the stationary-state kinetics eq 3 will hold. For this type of LRP, the PDI is more conveniently represented by (8) A B d d A 0 c 1 [YB - (I/ΧΠ,Β)]" = (kJkp)[c/(2 - c)] where c is the conversion.

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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