By Allen Noshay
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Extra info for Block Copolymers. Overview and Critical Survey
In addition to characterizing the total block copolymer, it is important to also determine the molecular structure of the segments themselves. This is possible with some block copolymers prepared via well-controlled synthetic techniques, such as living polymerization and the interaction of mutually reactive oligomers. In living polymerizations, samples may be withdrawn after each sequential monomer addition cycle for subsequent characterization. In the mutually reactive oligomer case, the starting components can be carefully characterized before use.
One of the better ways to investigate this phenomenon is density gradient ultracentrifugation. Assuming the 52 4. BLOCK COPOLYMER SYNOPSIS two components possess different densities, a bimodal distribution will be detected in the blend, while the block copolymer will have a single intermediate density and hence display a single mode distribution. Gel permeation chromatography (GPC), a more commonly used technique for measuring molecular weight distribution, can also be used for this purpose. However, since this technique is based on separation according to molecular size, it can only be used to detect bimodal distributions in blends in which the components are widely different in molecular size.
Since this chapter serves as a summary and guide, the references quoted in it are principally to the other sections of the book. A. SYNTHESIS 1. General Background Many approaches for synthesizing polymers with "blocklike" character have been reported. However, only a few actually are capa30 A. SYNTHESIS 31 ble of producing legitimate block copolymer structures. Others do not result in predictable or well-controlled architecture. The latter is exemplified by the random interaction of two high molecular weight homopolymers by means of mastication or interchange reactions and also by copolymers produced by free radical initiation.
Block Copolymers. Overview and Critical Survey by Allen Noshay