Molecular “recognition” in interpolymer interactions and matrix polymerization

Abstract

Results of theoretical and experimental investigations into selectivity in interpolymer reactions (molecular recognition) and the role played by this selectivity in the reactions of matrix synthesis of polymers have been systematized and generalized in this review. This fundamental property of interpolymer interactions — molecular recognition — results from the exponential dependence of polycomplex stability on the lengths of interacting chains. Recognition is manifested in the selectivity of interpolymer interactions with regard to the length and the structure of the chains which, under certain conditions, allow us to fractionate efficiently non-uniform polymers as well as polymer mixtures. Inversion of molecular recognition is possible when different polymer partners are recognized under different conditions. The mechanism of molecular recognition reactions (kinetics and mechanism of substitution and exchange reactions with participation of polycomplexes and free chains) is considered. As a necessary matrix-process step of polymer synthesis, molecular recognition of macromolecular-matrices by the growing daughter chains has an influence on the kinetics of these processes and on the structure of the daughter chains. In systems of two or more matrices with different chemical structures, molecular recognition predetermines the growth of daughter chains only on one (the strongest) matrix. Systems are considered in which, under certain conditions, matrix regeneration is possible in the process of matrix synthesis (i.e. freeing of the matrix from the polycomplex being formed) and multiple use of a single matrix for controlling the growth of the daughter chains.