Polymer Science, Early synthesis

In the early days of polymer science, when polystyrene became a commercial product, insolubility was sometimes observed which was not expected from the functionality of this monomer. Staudinger and Heuer [2] could show that this insolubility was due to small amounts of tetrafunctional divinylbenzene present in styrene as an impurity from its synthesis. As little as 0.02 mass % is sufficient to make polystyrene of a molecular mass of 2001000 insoluble [3]. This knowledge and the limitations of the technical processing of insoluble and non-fusible polymers as compared with linear or branched polymers explains why, over many years, research on the polymerization of crosslinking monomers alone or the copolymerization of bifunctional monomers with large fractions of crosslinking monomers was scarcely studied. 

The key word in the early years of polymer science is empiricism. Thus, Simon in 1839 made polystyrene but it was not until about 1937 with the recognition that high purity monomers were necessary to achieve desired polymer strength that the synthesis of industrially "satisfactory" polystyrene was achieved. 

The broad landscape of chemical topology and topoisomerism has been summarized in comprehensive reviews [2-5], The accomplishments of Schill, Walba, Sauvage, Stoddart, and others are landmarks in organic synthesis. This chapter describes a personal odyssey in which the focus is on statistical approaches - tinged by polymer science in their continual reference to the flexibility of chains. Some early laboratory efforts, and the technical considerations which led to them, are discussed, as is more recent activity. 

Attempts to use synthetic polymers in medicine can be traced to the early beginnings of polymer science. Even the recent literature devoted to this topic would represent a remarkable library. Still, the utilization of purely synthetic soluble polymers in clinical practice has rarely progressed beyond the experimental phase. Nevertheless, every new achievement in polymer synthesis has led to renewed attempts to develop... 

The chemistry of silyl radicals in the last decade has expanded considerably. Silyl radicals play an important role in diverse areas such as organic synthesis, material science and polymer chemistry. Since the early works have already been reviewed by one of the authors1, the purpose of this chapter is to bring together all the recent developments. Furthermore,... 

Polypyrrole (PPy) was the center of great interest during the early development of the science and technology of polyconjugated materials [168]. Science has been somehow hindered by the complex chemistry associated with the synthesis of the polymer. On the other hand, because of its stability the technological applications of doped PPy have spanned a wide range of possible applications and in some cases have reached the commercial level. 

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