Polymer Networks Formed by Molecular Brushes: Scaling Theory

The theory of swelling of networks formed by crosslinked comb-shaped macromolecules (molecular brushes) in a good solvent is developed using the scaling method. It is shown that the equilibrium coefficient of swelling of such networks depends in a complex way on a set of characteristic molecular architectural parameters: the density of grafting and the length and number of side chains emanating from one branching point on the main chain. In particular, it is predicted that the replacement of the linear subchains of the network with molecular brushes of the same molecular weight in most cases leads to a decrease in the degree of swelling of the network. At a fixed length of the main chains of molecular brushes forming the network, the coefficient of swelling nonmonotonically depends on the length of the side chains, passing through a maximum when the spacers of the main chain reach the ultimate stretching.