Automatic continuous online monitoring of polymerization reactions (ACOMP) was adapted to the monitoring of acrylamide polymerization in inverse emulsions. This is the first application of ACOMP to heterogeneous phase polymerization. The conversion and reduced viscosity were monitored by continuously inverting and diluting the emulsion phase using a small reactor sample stream and a breaker surfactant solution, followed by UV absorption and viscometric detection. This inversion into a stable portion of the polymer/surfactant phase diagram is accomplished in tens of seconds, yielding dilute solutions containing acrylamide (Aam), polyacrylamide (PA), oil droplets, and small quantities of surfactant, initiator and other debris, and low molecular weight compounds. After establishing the means of making ACOMP measurements, a first application of the method is made to resolving some of the kinetic issues involved in emulsion polymerization, including the evolution of molecular mass, and the simultaneous action of an "intrinsic" initiator and an added chemical initiator.

Using automatic, continuous online monitoring of polymerization reactions (ACOMP) the final, divergent growth phase (FDGP) of the condensation polymerization of dimethylamine, epichlorohydrin, and ethylenediamine was monitored, which produced a highly ramified, polyelectrolytic polyamine. The weight average mass, M w, increased exponentially during the FDGP, whereas weight averaged intrinsic viscosity [η]w increased slowly, reaching a plateau. Multi-detector gel permeation chromatography (GPC) revealed that polymers of mass 20 000 to 106 are branched and self-similar, but above this mass, [η] increases less strongly with M. This appears to be due to higher order ramification, a precursor to gelation. The ACOMP trends in M w and [η]w provide direct online evidence of this process. It is shown computationally that a mere increase in polydispersity cannot explain this behavior. GPC showed the mass distribution becomes highly asymmetric as conversion increases. A plausible kinetic model for the distribution asymmetry is introduced, and a complementary model for the effects of higher order ramification on [η]w.