Prelude to Practice

A second and distinct era in the development of branched macromolecular architecture encompasses the time between 1940 to 1978, or approximately the next four decades. Kuhn 151 published the first report of the use of statistical methods for analysis of a polymer problem in 1930. Equations were derived for molecular weight distributions of degraded cellulose. Thereafter, mathematical analyses of polymer properties and interactions flourished. Perhaps no single person has affected linear and non-linear polymer chemistry as profoundly as P. J. Flory. His contributions were rewarded by receipt of the Nobel Prize for Chemistry in 1974. 

Stockmayer 25 subsequently developed equations relating to branched-chain polymer size distributions and gel formation, whereby branch connectors were of unspecified length and branch functionality was undefined. An equation was derived for the determination of the extent of reaction where a three-dimensional, network ( gel ) forms this relation was similar to Flory s, although it was derived using another procedure. Stockmayer likened gel formation to that of a phase transition and noted the need to consider (a) intramolecular reactions, and (b) unequal reactivity of differing functional groups. This work substantially corroborated Flory s earlier studies. 

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