Formation and Structure of Polyacrylamide Gels

Acrylamide and N,N-methylenebis(acry1amide) (AAm-Bis) copolymerization has been investigated in water at a monomer concentration of 1.8 w/v %. Conversion of monomer and pendant vinyl groups was measured as a function of the reaction time up to the onset of macrogelation. Experimental results indicate that 80% of pendant vinyl groups are consumed by cyclization reactions. When the monomer concentration was kept constant at 1.8%, the critical conversion a t the gel point shows a minimum a t 7.5 mol % Bis. The equilibrium degree of swelling of the polyacrylamide (PAAm) gels is independent of their crosslinker content. Calculation results show that the average reactivity of pendant vinyl groups for intermolecular links decreases as the Bis concentration increases. All these results suggest formation of PAAm microgels prior to the onset of macrogelation. As the reaction proceeds, microgels are connected to a macrogel through their peripheral pendant vinyls and radical ends, whereas those in their interior remain intact. The microgels seem to act as the junction points of the final inhomogeneous networks.