By Nicolay V Tsarevsky, Brent S Sumerlin, Phlipp Vana, Robson Storey, Yusuf Yagci, Peter Nesvadba, Bradford Wayland, Graeme Moad, Atsushi Goto

Content material: creation; Kinetic, thermodynamic and different facets of radical polymerization; primary facets of dwelling polymerization; Controlled/living radical polymerization within the presence of iniferters; Controlled/living radical polymerization mediated through strong 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 way 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

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1039/9781849737425-00001 Kinetics and Thermodynamics of Radical Polymerization 25 By b-scission, a macroradical is cleaved into a chain-end radical and a double-bond-terminated molecule. 18), a chain-end radical with degree of polymerization n is cleaved into a similar chain-end radical with degree of polymerization (n À 1) and a monomer molecule. This reaction is often referred to as depropagation, since it is the back reaction of a propagation step. For mZ1, b-scission of a midchain radical (typically mZ2 for an MCR produced via backbiting) produces an SPR of chain length n and a so-called macromonomer, MM, of chain length m.

Polymerizations of a-methyl-vinyl monomers always show a contribution of disproportionation. 3. The hydrogen atoms of the a-methyl-group are more prone to abstraction during the disproportionation reaction than the methylene hydrogen atoms. 4. Within a series of vinyl or a-methyl-vinyl monomers, l apparently decreases according to the radical stabilization ability of the substituent. 2 Termination Rate The rate law expression for termination in its simplest form is Rterm ¼ À dcR ¼ 2kt cR2  dt ð1:18Þ with the radical concentration cR and the termination rate coefficient, kt.

E. the value of kt decreases with increasing pressure. This observation can also be connected with the pressure dependency of the viscosity. 8 Activation energies and volumes for the termination rate coefficients of selected acrylates and methacrylates. 0a (40 1C) 192 193 192 194 a This activation volume is pressure dependent, the value is valid for the pressure range from 1000 to 1500 bar. e. e. allowing for increased rates of polymerization at elevated pressures. 7 Solvent Effects In general, solvent effects on kt are rather small.

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