Anionic polymerization complex architectural polymer

Hadjichristidis, N. Pitsikalis, M. Pispas, S. latrou, H. Polymers with complex architecture by living anionic polymerization. Chem. Rev. 2001, 101, 3747-3792. 

Among the two ionic polymerization techniques mentioned above, a living anionic polymerization should show the best possible control of polymer architecture and composition. Mono dispersed homopolymers, complex-block, graft, star, and miktoarm architectures have been accessible primarily by anionic polymerization methods [22]. They have been used to grow polymer brushes from various small particles such as silica gels graphite,carbon black, and flat surfaces [23-26]. Recent results have been reported on living anionic polymerizations on clay [27] and silica nanoparticles [28,29]. 

Polymers with Complex Architecture by Living Anionic Polymerization... 

Anionic polymerization has proven to be a very powerful tool for the synthesis of well-defined macromolecules with complex architectures. Although, until now, only a relatively limited number of such structures with two or thee different components (star block, miktoarm star, graft, a,to-branched, cyclic, hyperbranched, etc. (co)polymers) have been synthesized, the potential of anionic polymerization is unlimited. Fantasy, nature, and other disciplines (i.e., polymer physics, materials science, molecular biology) will direct polymer chemists to novel structures, which will help polymer science to achieve its ultimate goal to design and synthesize polymeric materials with predetermined properties. 

Living polymerization was discovered in anionic system by Szwarc (see p. 476) in 1950, which, as we shall see in Chapter 8, offers many bene ts including the ability to control molecular weight and polydispersity and to prepare block copolymers and other polymers of complex architecture. Many attempts have then been made to develop a living polymerization process with free-radical mechanism so that it could combine the virtues of living polymerization with versatility and convenience of free-radical polymerization. Considering the enormous importance and application potential of living/controlled radical polymerization techniques, these will be considered in detail in another chapter (Chapter 11) with a state-of-the art discussion on the subject. 

The synthesis of well-defined polymers and of complex polymer architectures has been greatly facilitated by recent developments in controlled radical polymerization, which has opened up new possibilities in the design and also in the preparation of functional nanostructures based on supramolecular assembly. Controlled radical polymerization is an attractive alternative to anionic polymerization for preparing polymeric building blocks of well-defined size and a low polydispersity index... 

Hadjichristidis N, Pitsikahs M, Pispas S, latrou H. Polymers with complex architecture by hving anionic polymerization. Chem Rev 2001 101 3747-3792. 

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