Metal complexes in controlled radical polymerization

Transition Metal Catalysis in Controlled Radical Polymerization: Atom Transfer Radical Polymerization

“…[45] It is recommended that the involvement of radicals in metal-catalyzed polymerizations should always be tested using the above criteria, since even a small change in the monomer, ligand, temperature, or solvent may favor other reactions. For example, Cu(PF 6 )/4 CH 3 CN generates cationic polymerization of styrene, [46] analogously the CuBr/2 Bpy complex also yields a cationic polymerization of p-methoxystyrene, [47] whereas it generates carbanions from diethyl 2-bromomalonate. [32] Recent developments in ATRP: There are three directions in the current development of ATRP.…”

Adsorption of linear and star-shaped poly(acrylic acid) to model surfaces formed by amphiphiles at the air/water interface

“…This prevents radical side reactions like termination, producing polymers with adjustable molecular weight and low polydispersity. [17][18][19] Since the initiator should preferably have a structure similar to the growing polymer chain, 2bromoisobutyric acid ethyl ester was used as a initiator for the linear chains.…”

Exploring the first steps of an electrochemically-triggered controlled polymerization sequence: Activation of alkyl- and benzyl halide initiators by an electrogenerated FeIISalen complex

“…Oxidative addition can take place (leading formally to R-M nþ1 t -X and therefore one may consider the formation of a carbon-metal bond rather than halogen abstraction as depicted in the general scheme. In the pioneering works devoted to ATRP, the oxidative addition route was often discarded because ATRP did not proceed in the presence of radical inhibitors such as galvinoxyl, and that was implicitly favoring that the initial step releases a free radical by halogen abstraction [18]. In this respect, a-diimine iron complexes have been found recently to promote distinct polymerization mechanisms with RX initiators, among which ATRP and CCT (Catalytic Chain Transfer), the latter sequence being based on the formation of a R-Fe III intermediate according to an ''organometallic mediated radical polymerization" [19][20][21].…”