A thorough understanding of the structure physical/mechanical properties of the polymers has made possible the molecular design of macromolecules for specific application needs. Several methods exist for polymer synthesis and processing. When it concerns homopolymers, each polymer structure is identified with a particular method for its realization. Depending upon the situation, one or more of the methods (polycondensation, cationic, anionic, or free radical technique) is sometimes resorted to. Each process has its own merits and demerits. The condensation method is applicable to only a few cases of condensation monomers. A variety of vinyl and cyclic monomers are polymerized by anionic and cationic processes. These processes have obvious disadvantages in the sense that they warrant rigorous polymerization conditions like the need for ultrapure monomers, absolute moisture/oxygen free atmosphere, and cryogenic temperatures which are often difficult to realize on an industrial scale. A recent trend in polymer preparation is therefore directed toward a free radical method. The method has the advantage that practically all vinyl monomers can be homo or copolymerized under relatively mild conditions. Further, there is often good control over the reaction parameters governing the kinetics of polymerization, and hence on the molecular characteristics of the resultant polymers.