Conductimetry is one of the online monitoring techniques employed for emulsion polymerization reactions, which can give continuous information about nucleation and growth of particles. The most important factor affecting conductivity sensors performance especially contacting (resistance) types is fouling. To investigate the consequences of fouling, four monomers with different tendencies for fouling were selected: methyl methacrylate, butyl acrylate, styrene, and butadiene. Two types of conductivity sensors were also selected to continuously measure conductivity: a two‐electrode sensor and an inductive sensor, and the performance of these sensors were evaluated based on some criteria such as conductivity behavior, amount of fluctuation, change in cell constant, repeatability, and status of the minimum of conductivity. The results obtained from the contacting sensor showed that fouling significantly decreased the performance of this sensor in different ways even in reaction mixtures having moderate fouling rates. However, the inductive conductivity sensor provided the possibility of reliably measuring conductivity during very high‐fouling and highly unstable emulsion polymerizations with very good repeatability. The capabilities of this sensor also allowed an exact recognition of the important points in the conductivity curves particularly the minimum of conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44446.

Continuous conductivity measurements were performed during the batch emulsion polymerization of butadiene along with kinetic and particle size measurements. The critical monomer conversion was obtained around 55% and the rate of polymerization was correlated to the surfactant concentration with an exponent of 0.35 which was not in agreement with the exponent offered by Smith and Ewart. In addition, the evolution of some particle‐related quantities such as particle size and number of particles during the three intervals of the emulsion polymerization and their agreements with Smith‐Ewart mechanism were investigated. The behavior of conductivity in the emulsion polymerization of butadiene normally containing a buffering agent was found to be completely different from the unbuffered one. Comparison of the conductivity profiles with the kinetic and particle‐related quantities represented that the conductivity of the reaction mixture is very sensitive to the changes in the particle size so that any small change in the forms of nucleation, growth, and coagulation is clearly observed in the conductivity profiles. Furthermore, the conductimetric data are capable of determining some important points during the polymerization such as the beginning of the reaction that can be important from the industrial process control point of view. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45262.