Modeling of Polymer Network Formation from Preformed Precursors

Statistical and kinetic methods of modeling of polymer networks formation from pre‐prepared precursors are described and illustrated. Such precursors are characteristic of distributions of molecular weight and numbers of reactive groups of distinguishable type and reactivity, and contain branch points which get elastically active in the crosslinking stage. The examples include telechelic polymers with functionality distribution, functional copolymers composed of functional and non‐functional units and groups of different reactivity. The basics of statistical and kinetic network formation methods are outlined and their adaptation to cover the non‐uniform collection of precursor molecules as one of the components. The distributions of properties of the precursors are expressed by probability generating functions which serve as input for the crosslinking stage. Precursors of crosslinked polymeric materials are pre‐prepared from small molecules and are characteristic of distributions of composition, molecular weights, number, type, and reactivity of functional groups. These distributions depend on the history of precursor formation and affect the structure and properties of the final network.