Kinetics of Controlled/Living Radical Polymerization in Emulsified Systems

Abstract

AbstractSummary: For the controlled/living radical polymerization (CLRP) in which the active period during the chain formation is extremely small, ϕA < 1, such as the cases of usual SFRP and ATRP, the polymerization rate can be made larger by increasing the average number of monomeric units added during a single active period, $\bar P_{n,SA}$. The $\bar P_{n,SA}$‐value is inversely proportional to the trapping agent concentration [X], and the polymerization rate is controlled by [X]. For small particles, even with a single trapping agent, [X] in the particle could be larger than that in corresponding bulk polymerization, and the polymerization rate decreases with D, where Dp is the particle diameter. On the other hand, for CLRPs whose ϕA‐value is not very much smaller than unity, say ϕA>0.01, such as some of RAFT polymerization systems, the polymerization rate can be made larger by increasing the kinetic chain length for a given initiation frequency. For such reaction systems, the polymerization rate can be enhanced significantly by employing the emulsified polymerization systems.