Abstract
Fundamental principles to tackle the problems of design and control of polymeric networks formed in nonequilibrium reaction systems are elucidated, by taking free-radical copolymerization of vinyl and divinyl monomers as an example. In nonequilibrium polymerization systems, each primary polymer molecule is expected to experience different history of crosslinking reactions; i.e., the formed crosslinked structure is highly history-dependent. This feature enables one to control the resulting network structure by manipulating the reactor operations. In this article, we propose a kinetic model that provides a sound basis for controlling the network structure development, and the crosslinking density distribution that is an important feature of network formation in kinetically controlled systems is discussed. On the basis of the present model, comprehensive accounts are given for the computer simulation technique in which detailed structural analysis of network polymers can be conducted.
