Abstract
The early stages of the reversible addition/fragmentation transfer (RAFT) miniemulsion polymerization were simulated, focusing on the effect of the RAFT agent on droplet nucleation. For highly reactive RAFT agents, a large number of free radicals (Nc) needed to be captured by a droplet in order to initiate polymerization in the droplet, which was totally different from the behavior of regular miniemulsion polymerization. More interestingly, it was found that droplet size had a significant influence on Nc value. It was shown that the RAFT agent has a significant influence on miniemulsion polymerization, leading to long induction periods and retardation of polymerization. In addition, miniemulsion droplets with different sizes are nucleated at different times, which could lead to very low nucleation efficiency. The results would be very helpful in understanding and designing a RAFT miniemulsion polymerization system.
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