Dorota Greszta

CONTROLLED RADICAL POLYMERIZATION

Various methods which lead to the control of molecular weight and polydispersities, and which allow for the preparation of block copolymers by radical polymerization are discussed. Thermal polymerizationof styrenes in the presence of stable radicals, polymerization of vinyl acetate and methyl methacrylate in the presence of chromium complexed by macrocyclic ligands polymerization of vinyl acetate initiated by organoaluminum compounds complexed by dipyridyl and activated by stable radicals, as well as in the presence of phosphites, are described in detail.

Gradient copolymers by atom transfer radical copolymerization

Gradient copolymers, in which the instantaneous composition varies continuously along each chain, are discussed in terms of theoretical background, significance and examples from the literature. The specific focus is the use of atom transfer radical polymerization to synthesize gradient copolymers with various composition profiles. Examples of gradient copolymers using ionic and controlled radical polymerization techniques are presented. Atom transfer radical polymerization has been used under both batch and semi-batch conditions to produce gradient copolymers. The physical properties of gradient copolymers and possible future work in the field of gradient copolymers are discussed. Copyright

Atom Transfer Radical Polymerization Including Degenerative Transfer: Novel and General Pathways Towards “Living” / Controlled Radical Polymerization

A novel and general “living” radical polymerization, namely, Atom Transfer Radical Polymerization, ATRP, affords various pathways towards the synthesis of tailor — made (co)polymers with predetermined molecular weights up to Mn ≈ 105 and molecular weight distributions as narrow as 1.05. This paper describes four different approaches to “living” ATRP, i.e., iodide-based degenerative transfer, alkyl halide / transition metal species promoted halogen atom transfer, R-X / Mt n / Lx; radical initiator / transition metal species promoted halogen atom transfer, I-I / Mt n+1 / Lx; and alkyl halide/radical initiator / transition metal species promoted halogen atom transfer, R-X / I-I / Mt n+1 / Lx.