Swelling pressure and elastic behavior of polymacromonomer networks with different functionalities of junctions

Networks with different junction functionalities as obtained by polymerization of a macromonomer (composed of 20 units) at identical concentrations were studied by computer simulation. The functionality determined by the length of chains produced from the end units of the macromonomer was varied over a wide range by varying the kinetic parameters of polymerization. From the number of collisions of units with the lattice walls at different swelling stages, the network swelling pressure and the osmotic pressure of solution of its fragments obtained by cutting in half interjunction chains were determined. From these data, the osmotic and elastic components of swelling pressure were found, the former was defined as the pressure of solution and the latter was defined as the difference of the network and solution pressures. The osmotic component is a power function of the polymer concentration with the power index increasing from 2.7 to 3.9 with an increase in functionality from 4.8 to 55 in accordance with a change in network topology. The elastic pressure depends on the swelling ratio Q in different manners at a low and a high functionality of junctions. Its absolute value decreases with a growth in Q in the former case, in agreement with the theory of elasticity of phantom networks (∼Q−1/3), but increases in the latter case. This behavior is consistent with the effect of functionality on the elastic behavior of real polymacromonomer networks and confirms that differences in the character of change in the modulus of such networks during swelling are due to a difference in the functionality of their junctions. Possible mechanisms of the influence of multifunctional junctions on the elasticity of polymer networks are discussed.