Miniemulsion polymerization Living free radical

Living free-radical polymerization represents a promising technique to produce polymers with highly controlled structures. Different possible systems known from bulk polymerizations have been used in miniemulsions. The living free radical polymerization of, e.g., styrene via the miniemulsion approach allows one to eliminate the drawback of the bulk system where an increase in polydis-persity was found at high conversions due to the very high viscosity of the reaction medium [90]. 

Butte, A., Storti, G., and Morbidelli, M. (2001). Miniemulsion living free radical polymerization by RAFT. Macromolecules, 54(17) 5885-5896. 

Luo YW, Tsavalas J, Schork FJ. Theoretical aspects of particle swelling in living free radical miniemulsion polymerization. Macromolecules 2001 34 5501-5507. 

Living free radical polymerization is a unique technique used to prepare a variety of polymers with well-controlled molecular structures such as polymers with narrow molecular weight distribution, multiblock copolymers, and star polymers, which cannot be achieved by conventional free radical polymerization [77, 78]. This polymerization technique was originally investigated in homogeneous bulk and solution polymerization systems, and it has been successfully applied to heterogeneous miniemulsion polymerization system in the last decade [62,63]. 

Living free radical polymerizations were also carried out in miniemulsion systems via the reversible addition-fragmentation chain transfer mechanism [66]. The colloidal stability of miniemulsions is the key issue, and nonionic surfactants result in the best results. The polydispersity index of molecular weight distribution for the resultant miniemulsion polymer is generally smaller than 1.2. 

Stoffelbach, R, Griffete, N., Bui, C., Charleux, B. Use of a simple surface-active initiator in controlled/living free-radical miniemulsion polymerization under AGET tmd ARGET ATRP conditions. Chem. Commun. 39,4807- 809 (2008)... 

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