Rise of the Macromolecular Hypothesis

In an important paper published in 1920 Staudinger deplored the prevailing tendency to formulate polymeric substances as association compounds held together by partial valences.He specifically proposed the chain formulas 

Staudinger relentlessly championed the molecular, or primary valence, viewpoint in the years which followed. He supported his original contentions with the observation that hydrogenation of rubber, as well as its conversion to other derivatives, does not destroy its colloidal properties. In contrast to association colloids, high polymers (or macromolecules as he chose to call them ) exhibit colloidal properties in all solvents in which they dissolve. Polyoxymethylenes were ex- 

Staudinger s opposing view that the size of the crystallite bears no relationship to the size of the polymer molecule has been largely sub- 

Scarcely had the covalent chain concept of the structure of high polymers found root when theoretical chemists began to invade the field. In 1930 Kuhn o published the first application of the methods of statistics to a polymer problem he derived formulas expressing the molecular weight distribution in degraded cellulose on the assumption that splitting of interunit bonds occurs at random. 

The statistical approach has since assumed a dominant role in the treatment of the constitution, reactions, and physical properties of polymeric substances. The complexities of high polymers are far too great for a direct mechanistic deduction of properties from the detailed structures of the constituent molecules even the constitution of 

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