By Nicolay V Tsarevsky, Brent S Sumerlin, Phlipp Vana, Robson Storey, Yusuf Yagci, Peter Nesvadba, Bradford Wayland, Graeme Moad, Atsushi Goto
Content material: advent; Kinetic, thermodynamic and different features of radical polymerization; primary features of dwelling polymerization; Controlled/living radical polymerization within the presence of iniferters; Controlled/living radical polymerization mediated through sturdy radicals; Organometallic controlled/living radical polymerization; Controlled/living radical polymerizations within the presence of tellurium, antimony, and bismuth compounds; Reversible addition-fragmentation chain move (RAFT) polymerization; Degenerative move polymerization in accordance with iodine compounds and reversible chain move catalyzed polymerization mediated by means of germanium, tin and phosphorus compounds; Atom move radical polymerization (ATRP)
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Extra info for Fundamentals of controlled/living radical polymerization. Tsarevsky and Brent S. Sumerlin, Nicolay V. Tsarevsky and Brent S. Sumerlin
Sample text
A lowering of molecular mass, as may be expected from the ideal kinetic chain-length (ratio between propagation and termination rate) in conjunction with chain-end radical kp, is generally observed due to the decreased propagation reactivity of radical species (MCR) produced by transfer to polymer (see above). Further, short- and long-chain branches are introduced in the chains. Transfer to polymer is thermodynamically favored as the position of the radical at the chain-end is less stabilized as compared to a radical position along the polymer backbone.
This corresponds to a two or threefold rate increase in rate for a 10 1C temperature increase. Photochemical polymerization rates have a much lower activation energy of about 20 kJ molÀ1, according to close to zero activation energy of the photoinitiation process. A deviation from ideality in conventional radical polymerization, which is often observed and which also occurs frequently in controlled radical polymerization, is the effect of inhibition and retardation. These effects are due to reactions of macroradicals with transferring or terminating species.
Termination via RD, with rate coefficient kt,RD, occurs by chain-end encounter after successive addition of monomer units. This mechanism plays a major role when macroradicals are immobilized (trapped) in a polymer network. 20). 142,147 This method provides access to chain-length-averaged termination rate coefficients, hkti. 5 for bulk polymerization of MMA. The plot of hkti vs. 5 reveals distinct regimes of rather different conversion dependencies, which can be assigned to hkti being controlled by specific termination mechanisms, denoted as SD, TD or RD control.